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stringclasses 6
values |
|---|---|---|---|---|---|
Among the four routes shown in the figure, which route is the shortest? How many steps does it have?
|
[
"Route B from retrosynthetic analysis using Reaxys is the shortest, with 5 steps",
"Route D from retrosynthetic analysis using Synthia is the shortest, with 7 steps",
"Route C from retrosynthetic analysis using CAS ChemPlanner is the shortest, with 4 steps",
"Route A from retrosynthetic analysis using Reaxys is the shortest, with 6 steps"
] | 0
|
{
"title": "Computer-Aided Retrosynthesis for Greener and Optimal Total Synthesis of a Helicase-Primase Inhibitor Active Pharmaceutical Ingredient",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c00624",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c00624"
}
|
4
|
|
In Forward Route C, intermediate C9 is treated with FeCl2 to obtain C12. What chemical transformation primarily occurs in this step? What is the role of FeCl2?
|
[
"Tert-butyl azidoformate (C11) in the presence of ferrous chloride forms a metal nitrene intermediate with concomitant release of N2, followed by imination of the thioether to give C12",
"Tert-butyl azidoformate (C11) undergoes single-electron reduction by FeCl2 to generate a nitrogen-centered radical with concomitant release of N2, followed by coupling of the thioether with the radical to give C12",
"Tert-butyl azidoformate (C11) under ferrous chloride catalysis forms a metal carboxylate intermediate with concomitant release of CO2, followed by oxidative amination of the thioether to give C12",
"Tert-butyl azidoformate (C11) coordinates with FeCl2 to form an iron–azide complex, and the intermediate inserts into the thioether bond via a carbene intermediate to give C12"
] | 0
|
{
"title": "Computer-Aided Retrosynthesis for Greener and Optimal Total Synthesis of a Helicase-Primase Inhibitor Active Pharmaceutical Ingredient",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c00624",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c00624"
}
|
1
|
|
In Route A, during the sulfide oxidation step in the synthesis of IM-204, which major oxidant is used?
|
[
"Sodium periodate (NaIO4)",
"Trifluoroacetic acid (TFA/ DCM)",
"PhI(OAc)2 and NH4(NH2COO)",
"Sodium methanethiolate (MeSNa)"
] | 0
|
{
"title": "Computer-Aided Retrosynthesis for Greener and Optimal Total Synthesis of a Helicase-Primase Inhibitor Active Pharmaceutical Ingredient",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c00624",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c00624"
}
|
0
|
|
In the synthesis of IM-204 in Figure A, what strategy is used to connect the two substituted phenyl rings?
|
[
"Use a Heck coupling to connect the two substituted phenyl rings",
"Use a C-N coupling to connect the two substituted phenyl rings",
"Use a Suzuki coupling to connect the two substituted phenyl rings",
"Use an Ullmann coupling to connect the two substituted phenyl rings"
] | 2
|
{
"title": "Computer-Aided Retrosynthesis for Greener and Optimal Total Synthesis of a Helicase-Primase Inhibitor Active Pharmaceutical Ingredient",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c00624",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c00624"
}
|
0
|
|
What is the E-SMILES of the final product?
|
[
"Cc1nc(N(C)C(=O)Cc2ccc(-c3cc(Br)ccc3F)cc2)sc1S(C)(=N)=O<sep>",
"Cc1nc(N(C)C(=O)Cc2ccc(-c3cc(F)ccc3F)cc2)sc1S(C)(=O)=O<sep>",
"Cc1nc(N(C)C(=O)Cc2ccc(-c3cc(F)ccc3F)cc2)sc1S(C)=O<sep>",
"Cc1nc(N(C)C(=O)Cc2ccc(-c3cc(F)ccc3F)cc2)sc1S(C)(=N)=O<sep>"
] | 3
|
{
"title": "Computer-Aided Retrosynthesis for Greener and Optimal Total Synthesis of a Helicase-Primase Inhibitor Active Pharmaceutical Ingredient",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c00624",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c00624"
}
|
5
|
|
How many different structures of 1 did the author use?
|
[
"9",
"5",
"19",
"6"
] | 3
|
{
"title": "Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c01381",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c01381"
}
|
0
|
|
List the three products shown in the figure that contain a CO₂Et ester group and their corresponding aryl ring substituents and yields.
|
[
"1) 3ac: p-methoxyphenyl substitution (p-MeO-C₆H₄), yield 45%; 2) 3ae: p-chlorophenyl substitution (p-Cl-C₆H₄), yield 61%; 3) 3aj: m-fluorophenyl substitution (m-F-C₆H₄), yield 55%.",
"1) 3ab: p-methylphenyl substitution (p-Me-C₆H₄), yield 92%; 2) 3ad: p-fluorophenyl substitution (p-F-C₆H₄), yield 70%; 3) 3af: p-bromophenyl substitution (p-Br-C₆H₄), yield 74%.",
"1) 3ab: p-methylphenyl substitution (p-Me-C₆H₄), yield 74%; 2) 3ag: p-trifluoromethylphenyl substitution (p-CF₃-C₆H₄), yield 51%; 3) 3aj: m-fluorophenyl substitution (m-F-C₆H₄), yield 55%.",
"1) 3ab: p-methylphenyl substitution (p-Me-C₆H₄), yield 74%; 2) 3ad: p-fluorophenyl substitution (p-F-C₆H₄), yield 92%; 3) 3af: p-bromophenyl substitution (p-Br-C₆H₄), yield 70%."
] | 3
|
{
"title": "Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c01381",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c01381"
}
|
0
|
|
Please briefly describe the overall reaction equation of this gold-catalyzed reaction and the reaction conditions used.
|
[
"This reaction is carried out at room temperature, using JohnPhosAuCl (5 mol %) and NaBArF₄ (5 mol %) as catalysts, in dichloromethane solvent, coupling vinyldiazo compound 1 with vinylsilane 2 in a 1:2 molar ratio to produce product 3, effecting C–N bond formation.",
"This reaction is carried out at low temperature, using JohnPhosAuCl (5 mol %) and NaBArF₄ (5 mol %) as catalysts, in dichloromethane solvent, coupling vinyldiazo compound 1 with vinylsilane 2 in a 1:2 molar ratio to produce product 3, effecting C–C bond formation.",
"This reaction is carried out at room temperature, using JohnPhosAuCl (5 mol %) and NaBArF₄ (5 mol %) as catalysts, in dichloromethane solvent, coupling vinyldiazo compound 1 with vinylsilane 2 in a 2:1 molar ratio to produce product 3, effecting C–C bond formation.",
"This reaction is carried out at room temperature, using JohnPhosAuCl (5 mol %) and NaBArF₄ (5 mol %) as catalysts, in dichloromethane solvent, coupling vinyldiazo compound 1 with vinylsilane 2 in a 1:2 molar ratio to produce product 3, effecting C–C bond formation."
] | 3
|
{
"title": "Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c01381",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c01381"
}
|
0
|
|
The product with the highest yield was prepared from 2 substituted by which group?
|
[
"para-fluorophenyl",
"para-trifluoromethylphenyl",
"ortho-fluorophenyl",
"H"
] | 0
|
{
"title": "Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c01381",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c01381"
}
|
0
|
|
Which substituent in 2 will lead to decreased stability?
|
[
"methyl",
"1-furanyl",
"phenyl",
"2-furanyl"
] | 3
|
{
"title": "Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c01381",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c01381"
}
|
3
|
|
According to Method A, which product has the highest yield?
|
[
"4c has the highest yield, 99%",
"4b has the highest yield, 99%",
"4q has the highest yield, 95%",
"4o has the highest yield, 97%"
] | 1
|
{
"title": "Gold-Catalyzed Regioselective Synthesis of Crowded Cyclopentadienes by Migratory Cycloisomerization of Vinylallenes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02035",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02035"
}
|
0
|
|
Briefly describe the overall reaction process from vinyallene 3 to product 4 in Method A
|
[
"Under catalysis by [IPrAu(CH3CN)]SbF6 (1.0 mol%), vinyallene 3 in DCE solvent (90 °C, 2–12 h) undergoes gold activation to form a carbene intermediate, followed by five-membered ring closure to give the substituted cyclopentadiene product 4.",
"Under catalysis by [IPrAu(CH3CN)]SbF6 (10 mol%), vinyallene 3 in DCE solvent (90 °C, 2–24 h) undergoes gold activation to form a carbene intermediate, followed by five-membered ring closure to give the substituted cyclopentadiene product 4.",
"Under catalysis by [IPrAu(CH3CN)]SbF6 (1.0 mol%), vinyallene 3 in DCE solvent (90 °C, 2–24 h) undergoes gold activation to form a carbene intermediate, followed by five-membered ring closure to give the substituted cyclopentadiene product 4.",
"Under catalysis by [IPrAu(CH3CN)]SbF6 (1.0 mol%), vinyallene 3 in DCM solvent (90 °C, 2–24 h) undergoes gold activation to form a carbene intermediate, followed by five-membered ring closure to give the substituted cyclopentadiene product 4."
] | 2
|
{
"title": "Gold-Catalyzed Regioselective Synthesis of Crowded Cyclopentadienes by Migratory Cycloisomerization of Vinylallenes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02035",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02035"
}
|
2
|
|
If the substrate introduces a strongly electron-withdrawing group (such as p-CF3), what effect will it have on the reaction yield?
|
[
"Introducing a strongly electron-withdrawing group (such as p-CF3) into the substrate increases the yield.",
"Introducing a strongly electron-withdrawing group (such as p-CF3) into the substrate will cause the yield to decrease, for example 57% for 4g.",
"Introducing a strongly electron-withdrawing group (such as p-CF3) into the substrate will cause the yield to drop sharply, for example the yield of 4g falls to 25%.",
"Introducing a strongly electron-withdrawing group (such as p-CF3) into the substrate has almost no effect on the yield."
] | 1
|
{
"title": "Gold-Catalyzed Regioselective Synthesis of Crowded Cyclopentadienes by Migratory Cycloisomerization of Vinylallenes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02035",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02035"
}
|
3
|
|
What are the main differences between Method A and Method B in terms of catalyst loading, substrate types, and reaction conditions?
|
[
"Method A uses vinyallene 3 as the substrate with a catalyst loading of 1.0 mol%, Method B uses propargyl ester 1 and alkynylsilane 2 as substrates with a catalyst loading of 2.5 mol%; both are carried out in DCE at 90 °C.",
"Method A uses vinyallene 3 as the substrate with a catalyst loading of 1.0 mol%, Method B uses propargyl ester 1 and alkynylsilane 2 as substrates with a catalyst loading of 2.5 mol%; both are carried out in DCE at 80 °C.",
"Method A uses vinyallene 3 as the substrate with a catalyst loading of 10 mol%, Method B uses propargyl ester 1 and alkynylsilane 2 as substrates with a catalyst loading of 2.5 mol%; both are carried out in DCE at 90 °C.",
"Method A uses vinyallene 3 as the substrate with a catalyst loading of 1.0 mol%, Method B uses propargyl ester 1 and alkynylsilane 2 as substrates with a catalyst loading of 2.5 mol%; both are carried out in DCM at 90 °C."
] | 0
|
{
"title": "Gold-Catalyzed Regioselective Synthesis of Crowded Cyclopentadienes by Migratory Cycloisomerization of Vinylallenes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02035",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02035"
}
|
3
|
|
What is the structural difference between products 4c and 4d? What different aryl substituents do their corresponding substrates have?
|
[
"The side-chain aryl group on the carbon attached to PivO in 4c is a p-OMe substituted phenyl ring, whereas the PivO side-chain aryl group in 4d is an o-F substituted phenyl ring.",
"The side-chain aryl group on the carbon attached to PivO in 4c is a p-OMe substituted phenyl ring, whereas the PivO side-chain aryl group in 4d is a p-F substituted phenyl ring.",
"The side-chain aryl group on the carbon attached to PivO in 4c is an o-OMe substituted phenyl ring, whereas the PivO side-chain aryl group in 4d is a p-F substituted phenyl ring.",
"The side-chain aryl group on the carbon attached to PivO in 4c is an m-OMe substituted phenyl ring, whereas the PivO side-chain aryl group in 4d is a p-F substituted phenyl ring."
] | 1
|
{
"title": "Gold-Catalyzed Regioselective Synthesis of Crowded Cyclopentadienes by Migratory Cycloisomerization of Vinylallenes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02035",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02035"
}
|
3
|
|
In the Scope of Alkynes section, what are the substituents R on the benzene rings of products 4b and 4c respectively? What are their yields?
|
[
"Product 4b: R = –OCH3, yield 58%; Product 4c: R = –CH3, yield 64%.",
"Product 4b: R = –Cl, yield 63%; Product 4c: R = –Ph, yield 53%.",
"Product 4b: R = –CF3, yield 35%; Product 4c: R = –CO2Me, yield 49%.",
"Product 4b: R = –CH3, yield 64%; Product 4c: R = –OCH3, yield 58%."
] | 3
|
{
"title": "Carbosulfonylation of Alkynes: A Direct Conversion of sp-C to sp3-C through Visible Light-Mediated 3-Component Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02700",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02700"
}
|
0
|
|
In the preparation of which compound was the Boc group removed?
|
[
"4m",
"4s",
"4q",
"4p"
] | 1
|
{
"title": "Carbosulfonylation of Alkynes: A Direct Conversion of sp-C to sp3-C through Visible Light-Mediated 3-Component Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02700",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02700"
}
|
0
|
|
Please describe the overall reaction process shown in Scheme 2 and the structural features of the generated products.
|
[
"This reaction is a three-component photocatalytic one-pot method: aromatic or aliphatic alkynes (1), sodium sulfonate salts (2) and carboxylic acids (3) couple in the presence of 4CzIPN photocatalyst (1 mol %), DMSO solvent, blue light (456 nm) irradiation and air, ultimately yielding sulfone products (4–7). The product molecular skeletons incorporate a sulfonyl group –SO2–Ar.",
"This reaction is a three-component photocatalytic one-pot method: aromatic or aliphatic alkynes (1), sodium sulfonate salts (2) and carboxylic acids (3) couple in the presence of 4CzIPN photocatalyst (1 mol %), DMSO solvent, blue light (456 nm) irradiation and under nitrogen atmosphere, ultimately yielding sulfone products (4–7). The product molecular skeletons incorporate a sulfonyl group –SO2–Ar.",
"This reaction is a three-component photocatalytic one-pot method: aromatic or aliphatic alkynes (1), sodium sulfonate salts (2) and carboxylic acids (3) couple in the presence of 4CzIPN photocatalyst (1 mol %), DMF solvent, blue light (456 nm) irradiation and under nitrogen atmosphere, ultimately yielding sulfone products (4–7). The product molecular skeletons incorporate a sulfonyl group –SO2–Ar.",
"This reaction is a three-component photocatalytic one-pot method: aromatic or aliphatic alkynes (1), sodium sulfonate salts (2) and carboxylic acids (3) couple in the presence of 4CzIPN photocatalyst (1 mol %), DMSO solvent, blue light (456 nm) irradiation and under nitrogen atmosphere, ultimately yielding thioether products (4–7). The product molecular skeletons incorporate a sulfonyl group –SO2–Ar."
] | 1
|
{
"title": "Carbosulfonylation of Alkynes: A Direct Conversion of sp-C to sp3-C through Visible Light-Mediated 3-Component Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02700",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02700"
}
|
2
|
|
What are the structural features of the photocatalyst used in the figure?
|
[
"The photocatalyst contains four N-carbazolyl groups and two cyano groups, with the cyano groups in the meta positions.",
"The photocatalyst contains four N-carbazolyl groups and two nitro groups, with the nitro groups in the meta positions.",
"The photocatalyst contains four N-phenyl groups and two cyano groups, with the cyano groups in the para positions.",
"The photocatalyst contains four N-carbazolyl groups and three cyano groups, with one cyano group in the ortho position."
] | 0
|
{
"title": "Carbosulfonylation of Alkynes: A Direct Conversion of sp-C to sp3-C through Visible Light-Mediated 3-Component Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02700",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02700"
}
|
0
|
|
Which product can be generated from estrone, and what is its yield?
|
[
"7c. Its yield is 51%",
"7a. Its yield is 41%",
"7d. Its yield is 62%",
"7b. Its yield is 41%+25%"
] | 1
|
{
"title": "Carbosulfonylation of Alkynes: A Direct Conversion of sp-C to sp3-C through Visible Light-Mediated 3-Component Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02700",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02700"
}
|
0
|
|
How many functionalized products were obtained from 3b?
|
[
"3",
"6",
"1",
"5"
] | 3
|
{
"title": "Difluoroalkylation of Tertiary Amides and Lactams by an Iridium-Catalyzed Reductive Reformatsky Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c00438",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c00438"
}
|
0
|
|
How was product 6 in Scheme 5 obtained? Please write the specific reagents and reaction conditions.
|
[
"Product 3b was reacted with NaBH4 (1.5 equiv) in MeOH at room temperature for 12 h, which reduced the ester to primary alcohol 6, yield 81%.",
"Product 3b was reacted with DIBAL-H (1.05 equiv) in CH2Cl2 at −78°C for 1 h, which reduced the ester to primary alcohol 6, yield 81%.",
"Product 3b was reacted with NaBH4 (1.5 equiv) in EtOH at room temperature for 24 h, which reduced the ester to primary alcohol 6, yield 81%.",
"Product 3b was reacted with LiAlH4 (1.5 equiv) in THF from 0°C to room temperature for 4 h, which reduced the ester to primary alcohol 6, yield 81%."
] | 2
|
{
"title": "Difluoroalkylation of Tertiary Amides and Lactams by an Iridium-Catalyzed Reductive Reformatsky Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c00438",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c00438"
}
|
0
|
|
In Scheme 5, why is KOH/MeOH hydrolysis used first and then HCl to obtain carboxylate 9?
|
[
"First use KOH/MeOH to saponify ester 3b to a carboxylic acid (forming a carboxylate or salt-type intermediate), then use strong acid HCl to provide an acidic environment, thereby obtaining the free carboxylic acid 9;",
"First use KOH/MeOH to remove impurities in the reaction, then use HCl to adjust the pH to facilitate extraction to obtain 9",
"First use KOH/MeOH to convert ester 3b into a methyl ester intermediate, then acidify with HCl to obtain 9",
"First use KOH/MeOH to decarboxylate ester 3b to generate an alkene, then protonate with HCl to obtain 9"
] | 0
|
{
"title": "Difluoroalkylation of Tertiary Amides and Lactams by an Iridium-Catalyzed Reductive Reformatsky Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c00438",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c00438"
}
|
1
|
|
Please briefly describe the reaction equation for the first step in Scheme 5: the Ir-catalyzed reductive coupling that synthesizes product 3b, including the main reactants, catalyst, reductant, and reaction conditions.
|
[
"Using N,N-dimethylbenzamide (1b), catalyzed by IrCl(CO)(PPh₃)₂ (1 mol%), with TMDS (1.5 equiv) in toluene (0.1 M) at room temperature for 20 min. Then add ethoxycarbonyl-α,α-difluoroalkene (2a'), warm slowly from 0 °C to room temperature, react for 20 min, to obtain the difluoro-substituted ester 3b, yield 67%.",
"Using N,N-dimethylbenzamide (1b), catalyzed by IrCl(CO)(PPh₃)₂ (1 mol%), with TMS (1.5 equiv) in toluene (0.1 M) at room temperature for 20 min. Then add ethoxycarbonyl-α,α-difluoroalkene (2a'), warm slowly from 0 °C to room temperature, react for 20 min, to obtain the difluoro-substituted ester 3b, yield 67%.",
"Using N,N-dimethylbenzamide (1b), catalyzed by IrCl(CO)(PPh₃)₂ (1 mol%), with TMDS (1.5 equiv) in benzene (0.1 M) at room temperature for 20 min. Then add ethoxycarbonyl-α,α-difluoroalkene (2a'), warm slowly from 0 °C to room temperature, react for 20 min, to obtain the difluoro-substituted ester 3b, yield 67%.",
"Using N,N-dimethylbenzamide (1b), catalyzed by IrCl(CO)(PPh₃)₂ (1 mol%), with TMDS (1.5 equiv) in toluene (0.1 M) at room temperature for 20 min. Then add ethoxycarbonyl-α,α-difluoroalkene (2a'), warm slowly from 0 °C to room temperature, react for 10 min, to obtain the difluoro-substituted ester 3b, yield 67%."
] | 0
|
{
"title": "Difluoroalkylation of Tertiary Amides and Lactams by an Iridium-Catalyzed Reductive Reformatsky Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c00438",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c00438"
}
|
0
|
|
Starting from product 3b, which downstream functionalized derivatives are shown in Scheme 5? Please list for each derivative the corresponding reagents, reaction conditions, and yields.
|
[
"3b can be sequentially converted to:\n• Alcohol 6: NaBH4 (1.5 equiv), EtOH, room temperature, 24 h, yield 81%;\n• Amide 7: NH3 (20 equiv), MeOH, room temperature, 24 h, yield 85%;\n• Carboxylate 9: KOH (1.0 equiv), MeOH, room temperature, 24 h, then HCl (10 equiv), 1,4-dioxane/ether, room temperature, 20 min, quantitative yield;\n• Alcohol 8: obtain 9 first, then PhMgBr (2.1 equiv), THF, 0 °C→room temperature, 3 h, yield 61%;\n• Enol ether 10: Tebbe reagent (4.0 equiv), pyridine (1.5 equiv), toluene/THF, −78 °C→room temperature, 2 h, yield 42%.",
"3b can be sequentially converted to:\n• Alcohol 6: NaBH4 (1.5 equiv), EtOH, room temperature, 24 h, yield 74%;\n• Amide 7: NH3 (20 equiv), MeOH, room temperature, 24 h, yield 78%;\n• Carboxylate 9: KOH (1.0 equiv), MeOH, room temperature, 24 h, then HCl (10 equiv), 1,4-dioxane/ether, room temperature, 20 min, yield 100%;\n• Alcohol 8: obtain 9 first, then PhMgBr (2.1 equiv), THF, 0 °C→room temperature, 3 h, yield 58%;\n• Enol ether 10: Tebbe reagent (4.0 equiv), pyridine (1.5 equiv), toluene/THF, −78 °C→room temperature, 2 h, yield 45%.",
"3b can be sequentially converted to:\n• Alcohol 6: NaBH4 (1.5 equiv), EtOH, room temperature, 24 h, yield 81%;\n• Amide 7: NH3 (15 equiv), MeOH, room temperature, 24 h, yield 85%;\n• Carboxylate 9: KOH (1.0 equiv), MeOH, room temperature, 24 h, then HCl (10 equiv), 1,4-dioxane/ether, room temperature, 20 min, quantitative yield;\n• Alcohol 8: obtain 9 first, then PhMgBr (2.1 equiv), THF, 0 °C→room temperature, 3 h, yield 61%;\n• Enol ether 10: Tebbe reagent (4.0 equiv), pyridine (1.5 equiv), toluene/THF, −78 °C→room temperature, 2 h, yield 42%.",
"3b can be sequentially converted to:\n• Alcohol 6: NaBH4 (1.5 equiv), EtOH, room temperature, 24 h, yield 81%;\n• Amide 7: NH3 (20 equiv), DMF, room temperature, 24 h, yield 85%;\n• Carboxylate 9: KOH (1.0 equiv), MeOH, room temperature, 24 h, then HCl (10 equiv), 1,4-dioxane/ether, room temperature, 20 min, quantitative yield;\n• Alcohol 8: obtain 9 first, then PhMgBr (2.1 equiv), THF, 0 °C→room temperature, 3 h, yield 61%;\n• Enol ether 10: Tebbe reagent (4.0 equiv), pyridine (1.5 equiv), toluene/THF, −78 °C→room temperature, 2 h, yield 42%."
] | 0
|
{
"title": "Difluoroalkylation of Tertiary Amides and Lactams by an Iridium-Catalyzed Reductive Reformatsky Reaction",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c00438",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c00438"
}
|
0
|
|
Briefly describe the overall mechanistic pathway of this NHC-catalyzed reaction, including the major intermediates.
|
[
"3a generates the NHC catalyst under the action of base, which then undergoes nucleophilic addition with 1a to give intermediate (I); after proton transfer it forms the aza-Breslow intermediate II, which then adds to 2a to give intermediate (III); subsequent proton transfer and elimination generate 3a while regenerating the NHC catalyst.",
"The NHC catalyst is generated under the action of base, which then undergoes nucleophilic addition with 1a to give intermediate (I); after proton transfer it forms the aza-Breslow intermediate II, which then adds to 2a to give intermediate (III); subsequent proton transfer and elimination generate 3a while regenerating the NHC catalyst.",
"The NHC catalyst is generated under the action of base, which then undergoes nucleophilic substitution with 1a to give intermediate (I); after proton transfer it forms the aza-Breslow intermediate II, which then adds to 2a to give intermediate (III); subsequent proton transfer and elimination generate 3a while regenerating the NHC catalyst.",
"The NHC catalyst is generated under the action of base, which then undergoes nucleophilic addition with 1a to give intermediate (I); after proton transfer it forms the aza-Breslow intermediate II, which then adds to 2a to give intermediate (III); subsequent rearrangement generates 3a while regenerating the NHC catalyst."
] | 1
|
{
"title": "N-Heterocyclic-Carbene-Catalyzed Imine Umpolung for the Cross-Coupling of Quinoxalin-2-ones with Isatins",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c01166",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c01166"
}
|
2
|
|
In the above NHC catalytic cycle, which step is most likely the rate-determining step? Please state the reason.
|
[
"The most likely rate-determining step is the nucleophilic attack of the NHC catalyst on 1a to form tetrahedral intermediate I, because this process requires overcoming the strong C=O bond and significant steric hindrance, resulting in the highest energy barrier.",
"The most likely rate-determining step is the proton transfer of tetrahedral intermediate I to generate aza-Breslow intermediate II, because proton migration and intermediate rearrangement involve high-energy bond reorganization and thus present the highest energy barrier.",
"The most likely rate-determining step is the nucleophilic addition of aza-Breslow intermediate II to diketone 2a, because this step requires disrupting the stable conjugated system of the diketone and forming a new carbon–carbon bond, giving the highest energy barrier and therefore the greatest effect on the reaction rate.",
"The most likely rate-determining step is the final proton transfer and elimination of 3a to release the product, because this process requires breaking the stable NHC–carbon bond and overcoming the high energy barrier for restoration of aromaticity."
] | 2
|
{
"title": "N-Heterocyclic-Carbene-Catalyzed Imine Umpolung for the Cross-Coupling of Quinoxalin-2-ones with Isatins",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c01166",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c01166"
}
|
2
|
|
What is the key structural feature of reaction product 3a?
|
[
"Product 3a forms a novel heterocyclic framework spliced from a six-membered heterocyclic unit and a five-membered heterocycle derived from substrate 2a, in which one carbonyl is converted into a hydroxyl group connected to the newly formed C–C bond and the pyridine ring.",
"Product 3a forms a novel heterocyclic framework spliced from a six-membered heterocyclic unit and a five-membered heterocycle derived from substrate 2a, in which one carbonyl is converted into a carboxyl group connected to the newly formed C–C bond and the pyrrole ring.",
"Product 3a forms a novel heterocyclic framework spliced from a five-membered heterocyclic unit and a five-membered heterocycle derived from substrate 2a, in which one carbonyl is converted into a hydroxyl group connected to the newly formed C–C bond and the pyrrole ring.",
"Product 3a forms a novel heterocyclic framework spliced from a six-membered heterocyclic unit and a five-membered heterocycle derived from substrate 2a, in which one carbonyl is converted into a hydroxyl group connected to the newly formed C–C bond and the pyrrole ring."
] | 3
|
{
"title": "N-Heterocyclic-Carbene-Catalyzed Imine Umpolung for the Cross-Coupling of Quinoxalin-2-ones with Isatins",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c01166",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c01166"
}
|
0
|
|
Why is the aza-Breslow intermediate II generated in the mechanism? What role does it play in the subsequent reaction?
|
[
"The aza-Breslow intermediate II is formed by coupling of the NHC and 2a, possesses very strong nucleophilicity, and can perform a nucleophilic attack on the electron-rich aromatic ring of substrate 1a, thereby promoting cleavage of a new C–C bond and driving the cyclization process.",
"The aza-Breslow intermediate II is generated by coupling of the NHC with substrate 1a, has significant basicity and aromaticity, and can activate the carbonyl of isoquinoline-2,3-dione 2a by protonation, thereby promoting formation of a new C–N bond and driving cyclization.",
"The aza-Breslow intermediate II is formed by coupling of the NHC and substrate 1a, has very strong nucleophilicity and conjugative stability, and can launch an effective nucleophilic attack on the electron-deficient isoquinoline-2,3-dione 2a, thereby promoting formation of a new C–C bond and driving the cyclization process.",
"The aza-Breslow intermediate II is formed by coupling with the NHC and substrate 1a, has strong electrophilicity and conjugative stability, and can undergo electrophilic addition with isoquinoline-2,3-dione 2a, thereby promoting formation of a new C–O bond and driving the cyclization process."
] | 2
|
{
"title": "N-Heterocyclic-Carbene-Catalyzed Imine Umpolung for the Cross-Coupling of Quinoxalin-2-ones with Isatins",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c01166",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c01166"
}
|
2
|
|
Write the Extended-SMILES (E-SMILES) representation of the starting substrate 1a in the reaction.
|
[
"N1(c2c(C)cc(C)cc2C)CN2CCCC2=N1<sep>",
"C(c1ccccc1)N1C(=O)[C@@](O)(c2nc3ccccc3n(C)c2=O)c2ccccc21<sep>",
"N1(Cc2ccccc2)C(=O)C(=O)c2ccccc21<sep>",
"Cn1c(=O)cnc2ccccc21<sep>"
] | 3
|
{
"title": "N-Heterocyclic-Carbene-Catalyzed Imine Umpolung for the Cross-Coupling of Quinoxalin-2-ones with Isatins",
"journal": "JACS AU",
"doi": "10.1021/jacsau.4c01166",
"url": "https://pubs.acs.org/doi/10.1021/jacsau.4c01166"
}
|
5
|
|
How many structurally different sulfur Ylide substrates are used in the figure?
|
[
"8",
"6",
"9",
"7"
] | 0
|
{
"title": "Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02204",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02204"
}
|
0
|
|
Please briefly describe the two-step process flow and reaction conditions of this reaction.
|
[
"Step 1: React aldehyde 1a with sulfoxonium ylide 2 in the presence of 20 mol% chiral catalyst, 20 mol% AcONa, and DCM at room temperature for 12 h; Step 2: Add the Wittig reagent Ph₃P=CHCO₂R to the resulting reaction mixture and continue to react at room temperature for 1 h to obtain product 4.",
"Step 1: React aldehyde 1a with sulfoxonium ylide 2 in the presence of 10 mol% chiral catalyst, 20 mol% AcONa, and CDCl₃ at room temperature for 24 h; Step 2: Add the Wittig reagent Ph₃PCHCO₂R to the resulting reaction mixture and continue to react at room temperature for 1 h to obtain product 4.",
"Step 1: React aldehyde 1a with sulfoxonium ylide 2 in the presence of 20 mol% chiral catalyst, 20 mol% AcONa, and CDCl₃ at room temperature for 12 h; Step 2: Add the Wittig reagent Ph₃PCHCO₂R to the resulting reaction mixture and continue to react at room temperature for 1 h to obtain product 4.",
"Step 1: React aldehyde 1a with sulfoxonium ylide 2 in the presence of 20 mol% chiral catalyst, 20 mol% AcONa, and CDCl₃ at 30 °C for 12 h; Step 2: Add the Wittig reagent Ph₃PCHCO₂R to the resulting reaction mixture and continue to react at 0 °C for 2 h to obtain product 4."
] | 2
|
{
"title": "Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02204",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02204"
}
|
2
|
|
What are the R² substituents in product 4? What are the product's E/Z and enantiomeric excess (ee)?
|
[
"R² includes EtO, MeO, n-BuO, i-BuO, t-BuO, allyloxy (allylO), benzyloxy (BnO), and phenyl (Ph), etc.; the products are mainly Z-isomers, E/Z > 9:1, with enantiomeric excess between 99%–100% ee.",
"R² includes EtO, MeO, n-BuO, i-BuO, allyloxy (allylO), benzyloxy (BnO), and phenyl (Ph), etc. (without t-BuO); the products are mainly E-isomers, E/Z > 9:1, with enantiomeric excess between 70%–80% ee.",
"R² includes EtO, MeO, n-BuO, i-BuO, t-BuO, allyloxy (allylO), benzyloxy (BnO), and phenyl (Ph), etc.; the products are mainly E-isomers, E/Z > 9:1, with enantiomeric excess between 90%–97% ee.",
"R² includes EtO, MeO, n-PrO, i-BuO, t-BuO, allyloxy (allylO), benzyloxy (BnO), and phenoxy (PhO), etc.; the products are mainly Z-isomers, E/Z ≈ 1:1, with enantiomeric excess between 50%–60% ee."
] | 2
|
{
"title": "Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02204",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02204"
}
|
0
|
|
What catalyst and auxiliary base were used in this reaction? What were the amounts of each?
|
[
"The catalyst was a chiral prolinol derivative (the green structure in the figure), 10 mol%; the auxiliary base was sodium acetate (AcONa), 20 mol%.",
"The catalyst was a chiral prolinol derivative (the green structure in the figure), 20 mol%; the auxiliary base was sodium acetate (AcONa), 20 mol%.",
"The catalyst was a chiral prolinol derivative (the green structure in the figure), 20 mol%; the auxiliary base was triethylamine (Et3N), 20 mol%.",
"The catalyst was a chiral prolinol derivative (the green structure in the figure), 20 mol%; the auxiliary base was potassium carbonate (K2CO3), 20 mol%."
] | 1
|
{
"title": "Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02204",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02204"
}
|
0
|
|
What is the E-SMILES of reaction product 4?
|
[
"*OC(/C=C/[C@@H]1[C@@H](C(*)=O)[C@@H]1C1C(O)=CC=CC=1)=O<sep><a>0:R</a><a>8:R[2]</a>",
"*OC(/C=C/[C@@H]1[C@@H](C(*)=O)[C@@H]1C1C(O)=CC=CC=1)=O<sep><a>1:R</a><a>8:R[2]</a>",
"O(C)C(=O)/C=C/[C@@H]1[C@@H](C(=O)OC)[C@@H]1c1ccccc1O<sep>",
"c1(C(=O)[C@@H]2[C@@H](c3ccccc3O)[C@H]2/C=C/C(=O)OCC)ccccc1<sep>"
] | 0
|
{
"title": "Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c02204",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c02204"
}
|
5
|
|
Compare the yields and regioselectivities (dr) of products 3ba, 3ca, and 3da, which correspond to substrate 1 bearing different aryl substituents (such as Cl, Me, OMe). How do electronic properties affect the reaction's performance?
|
[
"Product (3ba) is the substrate 1 phenyl ring para-substituted by a weak electron-withdrawing chlorine, yield 71%, dr 83:17; product (3ca) is the substrate 1 phenyl ring para-substituted by an electron-donating methyl group, yield 62%, dr 82:18; product (3da) is the substrate 1 phenyl ring para-substituted by a strongly electron-donating methoxy group, yield 63%, dr 89:11. Overall, it can be seen that strongly electron-donating substitution is conducive to improving regioselectivity, while electron-withdrawing substitution is more helpful in increasing yield.",
"Product (3ba) is the substrate 1 phenyl ring para-substituted by a weak electron-withdrawing chlorine, yield 63%, dr 89:11; product (3ca) is the substrate 1 phenyl ring para-substituted by an electron-donating methyl group, yield 62%, dr 82:18; product (3da) is the substrate 1 phenyl ring para-substituted by a strongly electron-donating methoxy group, yield 71%, dr 83:17. Overall, it can be seen that electron-withdrawing substitution on the phenyl ring of substrate 1 may improve the reaction's regioselectivity, while electron-donating substitution may increase product yield.",
"Product (3ba) is the substrate 1 phenyl ring para-substituted by a weak electron-withdrawing chlorine, yield 63%, dr 83:17; product (3ca) is the substrate 1 phenyl ring para-substituted by an electron-donating methyl group, yield 62%, dr 89:11; product (3da) is the substrate 1 phenyl ring para-substituted by a strongly electron-donating methoxy group, yield 71%, dr 82:18. Overall, it can be seen that electron-donating substitution can increase both yield and selectivity.",
"Product (3ba) is the substrate 1 phenyl ring para-substituted by a weak electron-withdrawing chlorine, yield 62%, dr 82:18; product (3ca) is the substrate 1 phenyl ring para-substituted by an electron-donating methyl group, yield 63%, dr 89:11; product (3da) is the substrate 1 phenyl ring para-substituted by a strongly electron-donating methoxy group, yield 71%, dr 83:17. Overall, it can be seen that electron-withdrawing substitution is more conducive to yield enhancement, while electron-donating substitution is more conducive to regioselectivity."
] | 1
|
{
"title": "Stereoselective Synthesis of Densely Substituted Pyrrolidines via a [3+2] Cycloaddition Reaction between Chiral N-tert-Butanesulfinylazadienes and Azomethine Ylides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c02572",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c02572"
}
|
3
|
|
What is the E-SMILES of 3aa?
|
[
"[C@@H]1(C(=O)OC)[C@@H](c2ccccc2)[C@H](/C=N/[S@](C(C)(C)C)=O)[C@H](c2ccc(Br)cc2)N1<sep>",
"C(=O)(OC)[C@@H]1N[C@@H](c2ccc(Br)cc2)[C@@H](/C=N/[S@@](=O)C(C)(C)C)[C@@H]1c1ccccc1<sep>",
"C(=O)(OC)[C@H]1N[C@@H](c2ccccc2Br)[C@@H](/C=N/[S@@](=O)C(C)(C)C)[C@@H]1c1ccccc1<sep>",
"C(=O)(OC)[C@H]1N[C@@H](c2ccc(Br)cc2)[C@@H](\\C=N\\[S@@](=O)C(C)(C)C)[C@@H]1c1ccccc1<sep>"
] | 0
|
{
"title": "Stereoselective Synthesis of Densely Substituted Pyrrolidines via a [3+2] Cycloaddition Reaction between Chiral N-tert-Butanesulfinylazadienes and Azomethine Ylides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c02572",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c02572"
}
|
5
|
|
What kind of skeleton do the products obtained in Scheme 2 have? What is the naming rule for labels such as "3aa", "3ab", etc. in the figure?
|
[
"The products are substituted pyrrol-2-one-1-carboxylate derivatives, with the pyrrole ring bearing a sulfonyl group, an aryl group and an ester group, respectively. In the numbering \"3XY\", X refers to the index of substrate 2 (a–k), Y refers to the index of substrate 1 (a–g); the suffix \"'\" indicates the minor enantiomer.",
"The products are substituted pyrrolidine-2-carboxylate derivatives, with the five-membered ring bearing a sulfinyl group, an alkyl group and a hydroxyl group. In the numbering \"3XY\", X refers to the index of substrate 1 (a–g), Y refers to the index of substrate 2 (a–k); the suffix \"'\" denotes another stereoisomer.",
"The products are substituted pyrrolidine-2-formate ester derivatives, with the five-membered pyrrolidine ring bearing a sulfinyl group, an aryl group and an ester group, respectively. In the numbering \"3XY\", X refers to the index of the chiral auxiliary, Y refers to the index of substrate 2 (a–k); the suffix \"'\" indicates the trans isomer.",
"All products are substituted pyrrolidine-2-carboxylate derivatives, with the five-membered pyrrolidine ring bearing three substituents such as a sulfinyl group, an aryl group and an ester group. In the numbering \"3XY\", X refers to the index of substrate 1 (a–g), Y refers to the index of substrate 2 (a–k); the suffix \"'\", as in 3aa', indicates a regioisomer of the major product."
] | 3
|
{
"title": "Stereoselective Synthesis of Densely Substituted Pyrrolidines via a [3+2] Cycloaddition Reaction between Chiral N-tert-Butanesulfinylazadienes and Azomethine Ylides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c02572",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c02572"
}
|
0
|
|
What reaction conditions were used in this reaction? Please specify core elements such as the catalyst, solvent, and temperature.
|
[
"The reaction was carried out in toluene, using Ag2CO3 (10 mol%) as a basic co-catalyst, at room temperature (approximately 25 °C), with substrate 1 and substrate 2 mixed in a 2:1 molar ratio, the reaction concentration being about 0.4 M.",
"The reaction was carried out in toluene, using Ag2CO3 (10 mol%) as a basic co-catalyst, at room temperature (approximately 25 °C), with substrate 1 and substrate 2 mixed in a 1:2 molar ratio, the reaction concentration being about 0.4 M.",
"The reaction was carried out in toluene, using Ag2CO3 (1 mol%) as a basic co-catalyst, at room temperature (approximately 25 °C), with substrate 1 and substrate 2 mixed in a 1:2 molar ratio, the reaction concentration being about 0.4 M.",
"The reaction was carried out in toluene, using Ag2CO3 (10 mol%) as a basic co-catalyst, under heated conditions, with substrate 1 and substrate 2 mixed in a 1:2 molar ratio, the reaction concentration being about 0.4 M."
] | 1
|
{
"title": "Stereoselective Synthesis of Densely Substituted Pyrrolidines via a [3+2] Cycloaddition Reaction between Chiral N-tert-Butanesulfinylazadienes and Azomethine Ylides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c02572",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c02572"
}
|
0
|
|
What types of compounds are the two classes of substrates 1 and 2 shown in Scheme 2, and what are their structural features?
|
[
"Substrate 1 is a series of chiral N-tert-butanesulfinyl imines ((S)-N-tert-butanesulfinyl imine), whose sulfinyl nitrogen atom is substituted with t-Bu, and different alkyl groups are attached to the imine carbon; substrate 2 is a series of α-imino esters (α-imino ester), bearing an aryl group (Ar) and a hydroxyl group (–OH) on the two sides of the imino group, and can serve as acceptors for nucleophilic addition.",
"Substrate 1 is a series of chiral N-tert-butanesulfinyl imines ((S)-N-tert-butanesulfinyl imine), whose sulfinyl nitrogen atom is substituted with t-Bu, and different aryl groups are attached to the sulfinyl nitrogen; substrate 2 is a series of β-imino esters (β-imino ester), bearing an aryl group (Ar) and an ester group (–CO₂R⁴) on the two sides of the imino group, and can act as acceptors for nucleophilic addition.",
"Substrate 1 is a series of chiral N-tert-butanesulfinyl imines ((S)-N-tert-butanesulfinyl imine), whose sulfinyl nitrogen atom is substituted with t-Bu, and different aryl groups are attached to the imine carbon; substrate 2 is a series of α-imino esters (α-imino ester), bearing an aryl group (Ar) and an ester group (–CO₂R⁴) on the two sides of the imino group, and can act as acceptors for nucleophilic addition.",
"Substrate 1 is a series of chiral N-tert-butanesulfinamides ((S)-N-tert-butanesulfinamide), whose sulfonyl nitrogen atom is substituted with t-Bu, and different aryl groups are attached near the sulfinyl nitrogen; substrate 2 is a series of α-imino esters (α-imino ester), bearing an aryl group (Ar) and an ester group (–CO₂R⁴) on the two sides of the imino group, and can act as acceptors for nucleophilic addition."
] | 2
|
{
"title": "Stereoselective Synthesis of Densely Substituted Pyrrolidines via a [3+2] Cycloaddition Reaction between Chiral N-tert-Butanesulfinylazadienes and Azomethine Ylides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c02572",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c02572"
}
|
0
|
|
From the reaction type perspective, what kind of reaction is this?
|
[
"This reaction is an intermolecular asymmetric nucleophilic substitution reaction",
"This reaction is an intramolecular asymmetric rearrangement reaction",
"This reaction is an intramolecular asymmetric nucleophilic substitution reaction",
"This reaction is an intramolecular asymmetric nucleophilic addition reaction"
] | 2
|
{
"title": "Enantioselective Phase-Transfer-Catalyzed Synthesis of Spirocyclic Azetidine Oxindoles",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c00358",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c00358"
}
|
2
|
|
In Scheme 1D, what additional reagents and catalysts are introduced in the one-pot tandem procedure? Compared with preparing the halogenated intermediate first and then cyclizing, what advantages does this method have?
|
[
"In the D-stage reaction, the α-diazo substrate I is first cleaved by a Cu(I) catalyst to generate a metal carbene, and NBu₄⁺ (tetrabutylammonium salt) is added as an additive to effect cyclization to give III. This one-pot method can reduce catalyst loading, simplify workup, and slightly improve enantioselectivity, but does not significantly improve atom economy or reaction time.",
"In the D-stage reaction, the α-diazo substrate I is first cleaved by an Rh(III) catalyst to generate a metal carbene, which then undergoes cyclization in the presence of NR₄⁺ (quaternary ammonium salt) as an additive to give III. This one-pot method obviates the need to isolate the halogenated intermediate in advance, reduces operational steps, improves atom economy and time efficiency, while maintaining yields and er ratios comparable to the offline procedure.",
"In the D-stage reaction, the α-diazo substrate I is first cleaved by an Rh(II) catalyst to generate a metal carbene, which then undergoes cyclization in the presence of NR₄⁺ (quaternary ammonium salt) as an additive to give III. This one-pot method obviates the need to isolate the halogenated intermediate in advance, reduces operational steps, improves atom economy and time efficiency, while maintaining yields and er ratios comparable to the offline procedure.",
"The D-stage reaction uses an Rh(II) catalyst to cleave the α-diazo substrate I and, in the presence of carbonate ligands (such as potassium carbonate), introduces NR₄⁺ (quaternary ammonium salt) to promote cyclization to form III. This one-pot method does not require pre-isolation of the intermediate, can achieve higher diastereoselectivity at lower temperatures, but has time efficiency comparable to the offline procedure."
] | 2
|
{
"title": "Enantioselective Phase-Transfer-Catalyzed Synthesis of Spirocyclic Azetidine Oxindoles",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c00358",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c00358"
}
|
3
|
|
In Scope B, how does introducing different substituents on the aromatic ring (4-Me, 5-Me, 5-F, 7-F) affect yield and enantiomeric selectivity?
|
[
"4-Me substitution gives a yield of 65%, er = 16:84; 5-Me increases to 90%, er = 2:98; 5-F gives a yield of 88%, er = 3:97; 7-F gives a yield of 58%, er = 2:98.",
"4-Me substitution gives a yield of 69%, er = 14:86; 5-Me increases to 87%, er = 4:96; 5-F gives a yield of 89%, er = 2:98; 7-F gives a yield of 56%, er = 3:97.",
"4-Me substitution gives a yield of 69%, er = 14:86; 5-Me increases to 87%, er = 3:97; the electron-withdrawing 5-F position gives a yield of 92%, er = 2:98; 7-F decreases the yield to 56%, but the er remains 2:98.",
"4-Me substitution gives a yield of 78%, er = 12:88; 5-Me drops to 83%, er = 5:95; 5-F gives a yield of 94%, er = 1:99; 7-F gives a yield of 62%, er = 2:98."
] | 2
|
{
"title": "Enantioselective Phase-Transfer-Catalyzed Synthesis of Spirocyclic Azetidine Oxindoles",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c00358",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c00358"
}
|
3
|
|
Please write the general equation of the reaction shown in Scheme 1A, and indicate the key reaction conditions such as the substrate, product, catalyst, base, solvent, temperature, and time.
|
[
"The reaction converts the chloro-substituted N-protected ortho-amino amide (substrate II) into the five-membered/four-membered spiro lactam product (III) via an intramolecular SN2 cyclization in the presence of 20 mol% Cat7 and 5 equivalents of CsOAc, in m-xylene (0.1 M) at 25 °C for 1 h (900 rpm). Yields are mostly between 69-98%, with enantiomeric ratio (er) up to 19:1.",
"The reaction converts the chloro-substituted N-protected ortho-amino amide (substrate II) into the five-membered/four-membered spiro lactam product (III) via an intramolecular SN2 cyclization in the presence of 20 mol% Cat7 and 5 equivalents of CsOH, in m-xylene (0.1 M) at 25 °C for 1 h (900 rpm). Yields are mostly between 69-98%, with enantiomeric ratio (er) up to 9:1.",
"The reaction converts the chloro-substituted N-protected ortho-amino amide (substrate II) into the five-membered/four-membered spiro lactam product (III) via an intramolecular SN2 cyclization in the presence of 20 mol% Cat7 and 5 equivalents of CsOH, in p-xylene (0.1 M) at 25 °C for 1 h (900 rpm). Yields are mostly between 69-98%, with enantiomeric ratio (er) up to 19:1.",
"The reaction converts the chloro-substituted N-protected ortho-amino amide (substrate II) into the five-membered/four-membered spiro lactam product (III) via an intramolecular SN2 cyclization in the presence of 20 mol% Cat7 and 5 equivalents of CsOH, in m-xylene (0.1 M) at 25 °C for 1 h (900 rpm). Yields are mostly between 69-98%, with enantiomeric ratio (er) up to 19:1."
] | 3
|
{
"title": "Enantioselective Phase-Transfer-Catalyzed Synthesis of Spirocyclic Azetidine Oxindoles",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c00358",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c00358"
}
|
0
|
|
What is the E-SMILES of product 4?
|
[
"[N+](=O)([O-])c1ccc2c(c1)[C@]1(CCN1C(=O)OC(C)(C)C)C(=O)N2Cc1ccccc1<sep>",
"C1C=CC2N(*)C(=O)[C@@]3(N(*)CC3)C=2C=1<sep><r>0:Me</r><a>5:Bn</a><a>10:Boc</a>",
"COc1ccc2c(c1)[C@]1(CCN1C(=O)OC(C)(C)C)C(=O)N2Cc1ccccc1<sep>",
"COc1ccc2c(c1)[C@@]1(CCN1C(=O)OC(C)(C)C)C(=O)N2Cc1ccccc1<sep>"
] | 3
|
{
"title": "Enantioselective Phase-Transfer-Catalyzed Synthesis of Spirocyclic Azetidine Oxindoles",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c00358",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c00358"
}
|
5
|
|
How many steps in the figure have yields exceeding 90%?
|
[
"4",
"1",
"2",
"3"
] | 3
|
{
"title": "Biosourced Vanillin-Based Building Blocks for Organic Electronic Materials",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01869",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01869"
}
|
0
|
|
What are the reaction conditions and structural changes from molecule 5 to molecule 8?
|
[
"Using NaOH/MeOH as reagent, react at 70°C for 1 hour, causing the methyl ester group attached at the 2-position of the indole ring to be completely hydrolyzed to a carboxyl group, with the other functional groups remaining unchanged.",
"Using NaOH/MeOH-H2O as reagent, react at 70°C for 1 hour, causing the methyl ester group attached at the 2-position of the indole ring to be completely hydrolyzed to a carboxyl group, with the other functional groups remaining unchanged.",
"Using NaOH/MeOH-H2O as reagent, react at 70°C for 1 hour, causing the ethyl ester group attached at the 2-position of the indole ring to be completely hydrolyzed to a carboxyl group, with the other functional groups remaining unchanged.",
"Using NaOH/MeOH-H2O as reagent, react at 70°C for 1 hour, causing the methyl ester group attached at the 3-position of the indole ring to be completely hydrolyzed to a carboxyl group, with the other functional groups remaining unchanged."
] | 1
|
{
"title": "Biosourced Vanillin-Based Building Blocks for Organic Electronic Materials",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01869",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01869"
}
|
1
|
|
What is the overall reaction goal of Scheme 2?
|
[
"Scheme 2, through a series of steps including ester hydrolysis, thermal decarboxylation, N-methylation, and double-bond oxidation, ultimately synthesizes the target molecule pyridine derivative 11.",
"Scheme 2, through a series of steps including ester hydrolysis, thermal decarboxylation, N-methylation, and double-bond reduction, ultimately synthesizes the target molecule indole derivative 11.",
"Scheme 2, through a series of steps including ester hydrolysis, thermal decarboxylation, N-methylation, and double-bond oxidation, ultimately synthesizes the target molecule indole derivative 11.",
"Scheme 2, through a series of steps including ester hydrolysis, reduction, N-methylation, and double-bond oxidation, ultimately synthesizes the target molecule indole derivative 11."
] | 2
|
{
"title": "Biosourced Vanillin-Based Building Blocks for Organic Electronic Materials",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01869",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01869"
}
|
4
|
|
Which route from 9 to 11 has a higher yield?
|
[
"Equally high",
"Oxidize first, then methylate",
"Methylate first, then oxidize",
"Cannot be compared"
] | 2
|
{
"title": "Biosourced Vanillin-Based Building Blocks for Organic Electronic Materials",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01869",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01869"
}
|
3
|
|
Why is diphenyl ether (Ph2O) used and heated at 260 °C for 4 h in the step from molecule 8 to molecule 9? What kind of product is formed?
|
[
"The high-boiling diphenyl ether and the high temperature of 260 °C can effectively promote demethylation and aromatization of intermediate 8, producing pyrrole compound 9 with a yield of 80%.",
"The high-boiling diphenyl ether and the high temperature of 260 °C can effectively promote oxidative rearrangement of intermediate 8, producing an indazole compound 9 with a yield of 90%.",
"The high-boiling diphenyl ether and the high temperature of 260 °C can effectively promote thermal decarboxylation and aromatization of intermediate 8, producing an indole compound 9 with a yield of 87%.",
"The high-boiling diphenyl ether and the high temperature of 260 °C can effectively promote debromination and cyclization of intermediate 8, producing a furan compound 9 with a yield of 85%."
] | 2
|
{
"title": "Biosourced Vanillin-Based Building Blocks for Organic Electronic Materials",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01869",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01869"
}
|
1
|
|
Regarding the role of the membrane cell and unstirred conditions in reaction C, which of the following statements is correct?
|
[
"The membrane cell isolates the electrolyte from the electrode surface, preventing electrode passivation; not stirring reduces radical concentration and decreases side reactions.",
"The membrane cell separates the cathodic and anodic reaction regions, preventing intermediates or products from crossing between the two electrodes; not stirring slows solute diffusion, maintaining a high concentration of radicals at the electrode surface, improving selectivity and yield.",
"The membrane cell can adsorb intermediates, extending electrode lifetime; not stirring causes solute to deposit on the electrode surface, inhibiting formation of by-products.",
"The membrane cell increases the ion migration rate between electrodes, thereby accelerating the reaction rate; not stirring promotes uniform mixing of substances in the solution, improving selectivity."
] | 1
|
{
"title": "Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.0c02350",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.0c02350"
}
|
1
|
|
What are the electrochemical conditions and apparatus configuration used for Reaction C?
|
[
"In a divided cell (divided cell), without stirring, driven by alternating current (AC 3 V, sine wave, 2 Hz), the cathode and anode alternate polarity to achieve the reduction and oxidation half-reactions.",
"In a divided cell (divided cell), without stirring, driven by alternating current (AC 3 V, sine wave, 20 Hz), the cathode and anode alternate polarity to achieve the reduction and oxidation half-reactions.",
"In a divided cell (divided cell), with stirring, driven by alternating current (AC 3 V, sine wave, 2 Hz), the cathode and anode alternate polarity to achieve the reduction and oxidation half-reactions.",
"In a divided cell (divided cell), without stirring, driven by alternating current (AC 4 V, sine wave, 2 Hz), the cathode and anode alternate polarity to achieve the reduction and oxidation half-reactions."
] | 0
|
{
"title": "Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.0c02350",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.0c02350"
}
|
0
|
|
What type of electrochemical reaction does reaction C belong to?
|
[
"This reaction is a typical Kolbe coupling reaction, in which the amine is oxidized at the electrode to generate amine radicals, and then two amine radicals couple to form an N–N bond.",
"This reaction is an electrochemically promoted C–C cross-coupling reaction, in which the aryl bromide is reduced at the electrode to generate an aryl radical/anion intermediate, which then couples with another aryl radical to form a C–C bond producing biphenyl.",
"This reaction is an electrochemically promoted C–N cross-coupling reaction, in which the aryl bromide is reduced at the electrode to generate an aryl radical/anion intermediate, which then couples with an amine to form a C–N bond.",
"This reaction is an electrochemically promoted nucleophilic aromatic substitution reaction, in which the amine is oxidized at the electrode to generate an amine radical cation, which then performs a nucleophilic attack on the aryl bromide to form a C–N bond."
] | 2
|
{
"title": "Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.0c02350",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.0c02350"
}
|
2
|
|
Why does using alternating current (AC) give C–N coupled products, while under direct current (DC) conditions mainly aryl–aryl coupled dimer products are obtained?
|
[
"AC can continuously oxidize the amine at the anode to generate nitrogen cations, promoting their combination with aryl radicals; whereas DC overreduces the amine at the cathode, leading to depletion of the amine, so the aryl radicals can only couple with each other to form dimers.",
"AC can avoid electrode surface passivation, making the reaction between the amine and aryl radicals more efficient; under DC conditions cathode passivation is more severe, reducing the rate of amine generation, so the aryl radicals can only undergo self-coupling.",
"AC periodically reverses polarity, alternately generating amine radicals or anions and aryl radicals, facilitating their rapid capture and formation of C–N bonds; whereas DC continuously reduces aryl bromide, and the resulting aryl radicals are more prone to radical coupling to form C–C dimers.",
"AC produces high-voltage pulses that preferentially excite amine molecules to form cations, which then couple with aryl anions to form C–N bonds; DC maintains a steady potential and has difficulty exciting the amine, thereby causing aryl radicals to preferentially couple with each other to form C–C dimers."
] | 2
|
{
"title": "Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.0c02350",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.0c02350"
}
|
2
|
|
Write the E-SMILES of the reactant p-bromotrifluoromethylbenzene and the product N-(4-(CF3)phenyl)morpholine.
|
[
"p-Bromotrifluoromethylbenzene: C(c1ccc(Br)cc1)F(F)F<sep>\\nMorpholine: C1COCCN1<sep>\\nN-(4-(CF3)phenyl)morpholine: FC(F)(F)c1ccc(N2CCOCC2)cc1<sep>",
"p-Bromotrifluoromethylbenzene: C(c1ccc(Br)cc1)(F)(F)F<sep>\\nMorpholine: C1COCCN1<sep>\\nN-(4-(CF3)phenyl)morpholine: FC(F)(F)c1ccc(N2CCOCC2)cc1<sep>",
"p-Bromotrifluoromethylbenzene: C(c1ccc(Br)cc1)(F)(F)F<sep>\\nMorpholine: C1COCCN1<sep>\\nN-(4-(CF3)phenyl)morpholine: FC(F)(F)c1ccc(N2COCCN2)cc1<sep>",
"p-Bromotrifluoromethylbenzene: C(c1ccc(Br)cc1)(F)(F)F<sep>\\nMorpholine: C1CONCC1<sep>\\nN-(4-(CF3)phenyl)morpholine: FC(F)(F)c1ccc(N2CCOCC2)cc1<sep>"
] | 1
|
{
"title": "Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.0c02350",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.0c02350"
}
|
5
|
|
Describe the overall reaction equation and the structural features of the products shown in the figure.
|
[
"In the BMIm–BF4 electrolytic system, heating generates BF3 as the Lewis acid catalyst; phenol (1) and diethyl 2-oxopropanedioate (2) undergo a nucleophilic substitution–cyclization reaction, the main product being a fused bicyclic structure containing an oxygen heterocycle and an α-hydroxy ketone moiety (product 3), and a diester-substituted C-alkylation product (product 4) can also be obtained.",
"In the BMIm–BF4 electrolytic system, BF3 is generated in situ by electrolysis as the Lewis acid catalyst; phenol (1) and diethyl 2-oxopropanedioate (2) undergo a nucleophilic substitution–cyclization reaction, the main product being a fused bicyclic structure containing an oxygen heterocycle and an α-hydroxy ketone moiety (product 3), and a diester-substituted C-alkylation product (product 4) can also be obtained.",
"In the BMIm–BF4 electrolytic system, BF3 is generated in situ by electrolysis as the Lewis acid catalyst; phenol (1) and diethyl 2-oxopropanedioate (2) undergo a nucleophilic substitution–cyclization reaction, the main product being a fused bicyclic structure containing an oxygen heterocycle and an α-hydroxy ketone moiety (product 3), and a monoester-substituted C-alkylation product (product 4) can also be obtained.",
"In the BMIm–BF4 electrolytic system, BF3 is generated in situ by electrolysis as the Lewis acid catalyst; phenol (1) and dimethyl 2-oxopropanedioate (2) undergo a nucleophilic substitution–cyclization reaction, the main product being a fused bicyclic structure containing an oxygen heterocycle and an α-hydroxy ketone moiety (product 3), and a diester-substituted C-alkylation product (product 4) can also be obtained."
] | 1
|
{
"title": "In Situ Anodically Oxidized BMIm-BF4: A Safe and Recyclable BF3 Source",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c00932",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c00932"
}
|
2
|
|
How many phenolic substrates were screened in the table?
|
[
"11",
"1",
"2",
"3"
] | 3
|
{
"title": "In Situ Anodically Oxidized BMIm-BF4: A Safe and Recyclable BF3 Source",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c00932",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c00932"
}
|
0
|
|
Under the same BF₃ loading (30%), 50 °C, 4 h conditions, how do different R groups (4-OMe, H, 2-naphthol) affect the yield of product 3 and what are the reasons?
|
[
"When R = 4-OMe the yield is 79%, R = H is 86%, R = 2-naphthol is 88%. This indicates electron-donating and large π-conjugated substrates can both promote the reaction, while the neutral substrate has a slightly lower yield.",
"When R = 4-OMe the yield is 88%, R = H is 79%, R = 2-naphthol is 86%. This indicates a strong electron-donating group helps stabilize the intermediate and increase the yield, while the neutral substrate is unfavorable for nucleophilic aromatic cyclization.",
"When R = 4-OMe (electron-donating) the yield is 79%, R = H is 88%, R = 2-naphthol (large π-conjugation) is 86%. This indicates neutral or more extensively conjugated substrates are more favorable for nucleophilic aromatic cyclization, while an overly strong electron-donating methoxy group may cause side reactions or alter intermediate stability, slightly reducing the yield of the main product.",
"When R = 4-OMe the yield is highest (90%), R = H is next (85%), R = 2-naphthol is lowest (70%). This indicates a strong electron-donating effect is favorable for the reaction, while large π-conjugation instead inhibits cyclization."
] | 2
|
{
"title": "In Situ Anodically Oxidized BMIm-BF4: A Safe and Recyclable BF3 Source",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c00932",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c00932"
}
|
3
|
|
What are the key experimental conditions and procedures used in this reaction?
|
[
"Phenol (0.5 mmol) and diethyl ketomalonate (0.5 mmol) were added to a divided cell (BMIm–BF₄ as the electrolyte), and electrolyzed at a platinum electrode under an N₂ atmosphere at 10 A cm⁻² to generate BF₃. After electrolysis, the substrate was added to the anodic solution, stirred at the temperature (room temperature to 50 °C) and reaction time (2–24 h) shown in the table, and finally extracted with diethyl ether and purified by column chromatography to obtain the product.",
"Phenol (0.5 mmol) and diethyl ketomalonate (0.5 mmol) were added to a divided cell (BMIm–BF₄ as the electrolyte), and electrolyzed at a platinum electrode under an Ar atmosphere at 10 mA cm⁻² to generate BF₃. After electrolysis, the substrate was added to the anodic solution, stirred at the temperature (room temperature to 50 °C) and reaction time (2–24 h) shown in the table, and finally extracted with diethyl ether and purified by column chromatography to obtain the product.",
"Phenol (0.5 mmol) and diethyl ketomalonate (0.5 mmol) were added to a divided cell (BMIm–BF₄ as the electrolyte), and electrolyzed at a platinum electrode under an N₂ atmosphere at 10 mA cm⁻² to generate BF₃. After electrolysis, the substrate was added to the anodic solution, stirred at the temperature (room temperature to 50 °C) and reaction time (2–24 h) shown in the table, and finally extracted with ethyl acetate and purified by column chromatography to obtain the product.",
"Phenol (0.5 mmol) and diethyl ketomalonate (0.5 mmol) were added to a divided cell (BMIm–BF₄ as the electrolyte), and electrolyzed at a platinum electrode under an N₂ atmosphere at 10 mA cm⁻² to generate BF₃. After electrolysis, the substrate was added to the anodic solution, stirred at the temperature (room temperature to 50 °C) and reaction time (2–24 h) shown in the table, and finally extracted with diethyl ether and purified by column chromatography to obtain the product."
] | 3
|
{
"title": "In Situ Anodically Oxidized BMIm-BF4: A Safe and Recyclable BF3 Source",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c00932",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c00932"
}
|
0
|
|
Write the Extended SMILES (E-SMILES) of diethyl ketomaleate (substrate 2).
|
[
"O(CC)C(=O)C(=O)C(OCC)=O<sep>",
"O(C(=O)C(=O)C(OCC)=O)OC<sep>",
"O(C(=O)C(=O)C(OCC)=O)CC<sep>",
"O(C(=O)C(=O)C(OCC)=O)CC<sep><r>0:R</r>"
] | 2
|
{
"title": "In Situ Anodically Oxidized BMIm-BF4: A Safe and Recyclable BF3 Source",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c00932",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c00932"
}
|
5
|
|
How does the steric hindrance of the amine affect the yield? Please explain with reference to 3c and 3d.
|
[
"From 3c (yield 75%) and 3d (yield 31%), it can be seen that the larger the steric hindrance of the amine, the more difficult it is for it to nucleophilically attack the intermediate, resulting in a significant decrease in yield.",
"From 3c (yield 75%) and 3d (yield 31%), it can be seen that the larger the steric hindrance of the amine, the stronger its resonance effect, which increases nucleophilicity and, conversely, leads to a significant increase in yield.",
"From 3c (yield 75%) and 3d (yield 31%), it can be seen that the stronger the electron-donating effect of the amine, the more it will enhance the stability of the intermediate, which paradoxically leads to a decrease in yield.",
"From 3c (yield 75%) and 3d (yield 31%), it can be seen that cyclic substituents on the amine are more favorable for intermediate formation than linear substituents; therefore 3d's yield is higher than 3c's."
] | 0
|
{
"title": "Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c03993",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c03993"
}
|
3
|
|
Please describe in detail the steps and conditions of this amidation reaction.
|
[
"First react α-bromo hydrazone 1a with the amine (NHR2R3) in MeCN at 50 °C for 0.25 h, then add Et3N and continue the reaction for 0.5–1 h to afford the corresponding amide product.",
"First react α-bromo hydrazone 1a with Et3N in toluene at 50 °C for 0.25 h, then add the amine (NHR2R3) and continue under the same conditions for 0.5–1 h to give the corresponding amide product.",
"First react α-bromo hydrazone 1a with Et3N in MeCN at 25 °C for 1 h to generate an active intermediate; then add the amine (NHR2R3) and continue at 50 °C for 0.25 h to give the corresponding amide product.",
"First react α-bromo hydrazone 1a with Et3N in MeCN at 50 °C for 0.25 h to induce dehalogenation and generate an active intermediate; then add the amine (NHR2R3) at the same temperature and continue the reaction for 0.5–1 h to produce the corresponding amide products 3–4."
] | 3
|
{
"title": "Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c03993",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c03993"
}
|
2
|
|
Please provide the E-SMILES expression (Markush form) of the general formula of the product in this scheme.
|
[
"C(=O)(OC)[C@@H](NC(=O)CCCC)C(C)C<sep>",
"*C(N(*)*)=O<sep><a>0:R[1]</a><a>3:R[2]</a><a>4:R[3]</a>",
"*/C(=N/NC1C(*)=CC(Br)=CC=1)/Br<sep><a>0:R</a><a>6:NO2</a>",
"*C(N(*)*)=O<sep><a>0:R[1]</a><a>3:<dum></a><a>4:R[3]</a>"
] | 1
|
{
"title": "Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c03993",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c03993"
}
|
5
|
|
What reaction theme is shown in Scheme 2?
|
[
"This reaction is the substrate scope of nucleophilic aromatic substitution (SNAr Substrate Scope), namely the reaction system that uses α-bromohydrazone (hydrazonyl bromide) with various amines under basic conditions to generate arylamines via nucleophilic aromatic substitution.",
"This reaction is the substrate scope of reductive amination (Reductive Amination Substrate Scope), namely the reaction system that uses α-bromohydrazone (hydrazonyl bromide) with aldehydes in the presence of hydrogen or a reducing agent to produce secondary amines.",
"This reaction is the substrate scope of Suzuki coupling (Suzuki Coupling Substrate Scope), namely the reaction system that uses α-bromohydrazone (hydrazonyl bromide) with arylboronic acids under basic conditions to produce biaryl compounds.",
"This reaction is the substrate scope of amidation (Amidation Substrate Scope), namely the reaction system that uses α-bromohydrazone (hydrazonyl bromide) with various amines under basic conditions to produce amides."
] | 3
|
{
"title": "Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c03993",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c03993"
}
|
0
|
|
Why is the yield 0 when the amine is p-nitroaniline (corresponding to 3s)?
|
[
"The –NO2 on p-nitroaniline is a strong electron-withdrawing group that significantly reduces the nucleophilicity of the amine nitrogen, making it unable to effectively attack the intermediate, thereby preventing product formation and giving a zero yield.",
"The –NO2 on p-nitroaniline undergoes coupling side reactions during intermediate formation, producing insoluble material that clogs the reaction, resulting in a zero yield.",
"The –NO2 on p-nitroaniline reacts with Et3N to form a stable salt, causing the amine nitrogen to be blocked and unable to attack the intermediate, so the yield is zero.",
"In MeCN solvent at 50°C, the –NO2 on p-nitroaniline promotes oxidation of the amine itself to a nitroso compound, preventing normal amination and giving a zero yield."
] | 0
|
{
"title": "Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c03993",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c03993"
}
|
3
|
|
Please provide the Extended-SMILES (E-SMILES) representation of the reactant diethyl maleate.
|
[
"C(=O)(/C=C\\C(=O)OCC)OCC<sep>",
"C(OCC)(/C=C\\\\C(OCC)=O)=O<sep>",
"C(OCC)(/C=C\\\\C(OCC)O)=O<sep>",
"C(C(=O)OCC)C(=O)OCC<sep>"
] | 1
|
{
"title": "Moving Beyond Cyanoarene Thermally Activated Delayed Fluorescence Compounds as Photocatalysts: An Assessment of the Performance of a Pyrimidyl Sulfone Photocatalyst in Comparison to 4CzIPN",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.2c01137",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.2c01137"
}
|
5
|
|
What is the title of this reaction?
|
[
"Based on our experimental observations, the mechanism of the decarboxylative addition reaction of diethyl maleate with N-Boc-proline when using pDTCz-DPmS as the photocatalyst",
"Based on our experimental observations, the mechanism of the decarboxylative coupling reaction of diethyl maleate with N-Cbz-proline when using pDTCz-TPmS as the photocatalyst",
"Based on our experimental observations, the mechanism of the decarboxylative addition reaction of diethyl maleate with N-Cbz-proline when using pDTCz-DPmS as the photocatalyst",
"Based on our experimental observations, the mechanism of the decarboxylative addition reaction of dimethyl succinate with N-Cbz-proline when using pDTCz-DPmS as the photocatalyst"
] | 2
|
{
"title": "Moving Beyond Cyanoarene Thermally Activated Delayed Fluorescence Compounds as Photocatalysts: An Assessment of the Performance of a Pyrimidyl Sulfone Photocatalyst in Comparison to 4CzIPN",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.2c01137",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.2c01137"
}
|
2
|
|
What role does diethyl maleate play in the photocatalytic cycle? Why can it be reduced by PC* to generate a radical anion?
|
[
"Diethyl maleate donates a hydrogen atom to the excited-state PC* via hydrogen atom transfer, generating an α-carbon radical, which then couples to give the target product assisted by a carbanion intermediate.",
"Diethyl maleate acts as an energy transfer species exchanging energy with PC*, and its α,β-unsaturated double bond absorbs energy and cleaves to generate radicals, which then couple with the substrate.",
"Diethyl maleate acts as an electron donor and is oxidized by the excited-state PC*; the molecule's α,β-unsaturated double bond and adjacent ester groups help stabilize the resulting radical cation, promoting radical coupling.",
"Diethyl maleate acts as an electron acceptor and is reduced by the excited-state PC*; the molecule's α,β-unsaturated double bond and adjacent ester groups can stabilize the resulting radical anion, promoting radical coupling to form the target product."
] | 3
|
{
"title": "Moving Beyond Cyanoarene Thermally Activated Delayed Fluorescence Compounds as Photocatalysts: An Assessment of the Performance of a Pyrimidyl Sulfone Photocatalyst in Comparison to 4CzIPN",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.2c01137",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.2c01137"
}
|
1
|
|
Which of the following statements about the overall reaction process and the sequence of formation of key intermediates is correct?
|
[
"First, under visible light irradiation the pDTCz-DPmS photocatalyst (PC) is excited to the high-energy state PC*; PC* transfers an electron to diethyl maleate, generating the diethyl maleate radical anion; meanwhile, base deprotonates the N-Cbz-proline carboxylic acid to the carboxylate, and PC•+ oxidizes this carboxylate to a carboxyl radical which decarboxylates releasing CO₂ to give the N-Cbz-pyrrolidinyl radical; finally the diethyl maleate radical anion couples with the N-Cbz-pyrrolidinyl radical to give the decarboxylative addition product, while PC•+ recovers an electron and is reduced back to PC*, completing the catalytic cycle.",
"First, under visible light irradiation the pDTCz-DPmS photocatalyst (PC) is excited to the high-energy state PC*; PC* transfers an electron to dimethyl maleate, generating the dimethyl maleate radical anion; meanwhile, base deprotonates the N-Cbz-proline carboxylic acid to the carboxylate, and PC•+ oxidizes this carboxylate to a carboxyl radical which decarboxylates releasing CO₂ to give the N-Cbz-pyrrolidinyl radical; finally the dimethyl maleate radical anion couples with the N-Cbz-pyrrolidinyl radical to give the decarboxylative addition product, while PC•+ recovers an electron and is reduced back to PC, completing the catalytic cycle.",
"First, under visible light irradiation the pDTCz-DPmS photocatalyst (PC) is excited to the high-energy state PC*; PC* transfers an electron to diethyl maleate, generating the diethyl maleate radical anion; meanwhile, base deprotonates the N-Cbz-proline carboxylic acid to the carboxylate, and PC•+ oxidizes this carboxylate to a carboxyl radical which decarboxylates releasing CO₂ to give the N-Cbz-pyrrolidinyl radical; finally the diethyl maleate radical anion couples with the N-Cbz-pyrrolidinyl radical to give the decarboxylative addition product, while PC•+ recovers an electron and is reduced back to PC, completing the catalytic cycle.",
"First, under visible light irradiation the pDTCz-DPmS photocatalyst (PC) is excited to the high-energy state PC*; PC* transfers an electron to diethyl maleate, generating the diethyl maleate radical anion; meanwhile, base deprotonates the N-Boc-proline carboxylic acid to the carboxylate, and PC•+ oxidizes this carboxylate to a carboxyl radical which decarboxylates releasing CO₂ to give the N-Boc-pyrrolidinyl radical; finally the diethyl maleate radical anion couples with the N-Boc-pyrrolidinyl radical to give the decarboxylative addition product, while PC•+ recovers an electron and is reduced back to PC, completing the catalytic cycle."
] | 2
|
{
"title": "Moving Beyond Cyanoarene Thermally Activated Delayed Fluorescence Compounds as Photocatalysts: An Assessment of the Performance of a Pyrimidyl Sulfone Photocatalyst in Comparison to 4CzIPN",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.2c01137",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.2c01137"
}
|
2
|
|
Why convert the carboxylic acid of N-Cbz-proline to its carboxylate before performing photooxidation?
|
[
"The oxidation potential of the carboxylate is significantly lower than that of the non-deprotonated carboxylic acid, making it more easily single-electron oxidized by the excited photocatalyst (PC*) to generate a carboxyl radical intermediate, thereby efficiently triggering the subsequent decarboxylation and increasing the reaction rate.",
"The oxidation potential of the carboxylate is higher than that of the non-deprotonated carboxylic acid, which is unfavorable for single-electron oxidation by the excited PC*, so the reaction rate instead decreases.",
"The carboxylate forms hydrogen bonds with the excited PC*, directing an isomerization reaction pathway rather than decarboxylation, thereby changing the product distribution.",
"Converting the carboxylic acid to its carboxylate is mainly to increase the substrate's water solubility and enhance diffusion and collisions with PC*, but it does not greatly affect the oxidation potential."
] | 0
|
{
"title": "Moving Beyond Cyanoarene Thermally Activated Delayed Fluorescence Compounds as Photocatalysts: An Assessment of the Performance of a Pyrimidyl Sulfone Photocatalyst in Comparison to 4CzIPN",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.2c01137",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.2c01137"
}
|
1
|
|
How was product 6 prepared? Please describe in detail the two-step experimental operations and the reagents and conditions used.
|
[
"Step 1: TMSCN (in excess) was added in dichloromethane at room temperature, reacted for 1 h to generate the silanol hydrazone intermediate; Step 2: 2 M HCl and methanol were added to the reaction mixture, reacted at room temperature for 30 min to give product 6, overall yield 75%.",
"Step 1: TMSCN (in excess) was added in dichloromethane at room temperature, reacted for 2 h to generate the silanol hydrazone intermediate; Step 2: 2 M HCl and ethanol were added to the reaction mixture, reacted at room temperature for 30 min to give product 6, overall yield 75%.",
"Step 1: TMSCN (in excess) was added in dichloromethane at room temperature, reacted for 2 h to generate the silanol hydrazone intermediate; Step 2: 2 M HCl and methanol were added to the reaction mixture, reacted at room temperature for 30 min to give product 6, overall yield 75%.",
"Step 1: TMSCN (in excess) was added in dichloroethane at room temperature, reacted for 2 h to generate the silanol hydrazone intermediate; Step 2: 2 M HCl and methanol were added to the reaction mixture, reacted at room temperature for 30 min to give product 6, overall yield 75%."
] | 2
|
{
"title": "Palladium-Catalyzed Access to Benzocyclobutenone-Derived Ketonitrones via C(sp2)-H Functionalization",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c01317",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c01317"
}
|
4
|
|
In the preparation of which compound was a benzyne intermediate encountered?
|
[
"2v",
"2u",
"3",
"4"
] | 3
|
{
"title": "Palladium-Catalyzed Access to Benzocyclobutenone-Derived Ketonitrones via C(sp2)-H Functionalization",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c01317",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c01317"
}
|
2
|
|
In the tandem C–H activation/1,3-dipolar cycloaddition reaction, when dppe and rac-BINAP are used as ligands, what does the yield difference between products 2u and 2u' reflect?
|
[
"The different ligands' electronic and steric effects affect the selectivity of Pd-catalyzed insertion and dipolar cycloaddition. dppe has smaller steric hindrance, making the side product 2u' more easily formed; whereas rac-BINAP's larger steric bulk and chiral environment suppress the formation of 2u', increasing the yield of 2u (up to 55%) and producing almost no 2u'.",
"The different ligands' electronic effects are the main influencing factor. dppe's strong electron-donating effect promotes Pd insertion and cycloaddition to give 2u, whereas rac-BINAP's weaker electron-donating ability leads to a decreased yield of 2u and an increase in 2u'.",
"The different ligands' chiral induction effects are key. The achiral ligand dppe cannot induce stereoselectivity, leading to similar ratios of 2u and 2u'; whereas rac-BINAP's chiral environment strongly induces formation of 2u', significantly increasing the yield of 2u'.",
"Different ligand bite angles change the geometry at the Pd center, thereby directly affecting formation of 2u and 2u'. dppe's larger bite angle favors cycloaddition to give 2u, whereas rac-BINAP's smaller bite angle more readily produces 2u'."
] | 0
|
{
"title": "Palladium-Catalyzed Access to Benzocyclobutenone-Derived Ketonitrones via C(sp2)-H Functionalization",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c01317",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c01317"
}
|
3
|
|
What are the reactants, reaction conditions, and yield for generating product 3?
|
[
"The reactants are nitrone (2a) and N-methyl maleimide, reacted in toluene at 80 °C for 12 h, giving the target product 3 in 81% yield.",
"The reactants are nitrone (2a) and N-methyl maleimide, reacted in toluene at 80 °C for 2 h, giving the target product 3 in 81% yield.",
"The reactants are nitrone (2a) and maleimide, reacted in toluene at 80 °C for 2 h, giving the target product 3 in 81% yield.",
"The reactants are nitrone (2a) and N-methyl maleimide, reacted in benzene at 80 °C for 2 h, giving the target product 3 in 81% yield."
] | 1
|
{
"title": "Palladium-Catalyzed Access to Benzocyclobutenone-Derived Ketonitrones via C(sp2)-H Functionalization",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c01317",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c01317"
}
|
0
|
|
What is the title of the first reaction in Scheme 3? Which two main reaction types does it belong to?
|
[
"The reaction title is \"1,3-dipolar cycloaddition and redox reaction\", mainly involves the 1,3-dipolar cycloaddition of a nitrone with N-methyl maleimide and the subsequent redox-driven ring-opening process.",
"The reaction title is \"1,3-dipolar cycloaddition and ring-opening reaction\", mainly involves the 1,3-dipolar cycloaddition of a nitrone with N-methyl maleimide and the subsequent ring-strain-driven ring-opening process.",
"The reaction title is \"1,3-dipolar cycloaddition and ring-contraction reaction\", mainly involves the 1,3-dipolar cycloaddition of a nitrone with N-phenyl maleimide and the subsequent ring-strain-driven ring-contraction process.",
"The reaction title is \"1,3-dipolar cycloaddition and nucleophilic addition reaction\", mainly involves the 1,3-dipolar cycloaddition of a nitrone with N-methyl maleamide and the subsequent nucleophilic ring-opening process."
] | 1
|
{
"title": "Palladium-Catalyzed Access to Benzocyclobutenone-Derived Ketonitrones via C(sp2)-H Functionalization",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.2c01317",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.2c01317"
}
|
0
|
|
During the preparation of which compound is a low-temperature reaction required?
|
[
"3",
"4",
"6",
"5"
] | 2
|
{
"title": "Chemo-, Regio-, and Stereoselective cis-Hydroboration of 1,3-Enynes: Copper-Catalyzed Access to (Z,Z)- and (Z,E)-2-Boryl-1,3-dienes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c01929",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c01929"
}
|
0
|
|
Please summarize the four derivatization reactions (a–d) centered on 2-boryl-1,3-diene 2f in Scheme 4 and their corresponding products (3–6).
|
[
"Scheme 4 shows four reaction pathways starting from 2-boryl-1,3-diene 2f:\na) KHF₂/AcOH effects removal of Bpin to give the deborylated product 3 (yield 54%, >99∶1 Z∶E);\nb) Pd₂(dba)₃/SPhos-catalyzed Suzuki coupling with 4-iodobenzonitrile affords the arylated product 4 (yield 74%, >95∶5 Z∶E);\nc) H₂O₂/NaOH oxidation of the boronate gives the α,β,γ,δ-unsaturated ketone product 5 (yield 54%, >99∶1 Z∶E);\nd) nBuLi/CH₂Br₂ insertion followed by H₂O₂ oxidation provides the allylic alcohol product 6 (yield 40%, >99∶1 Z∶E).",
"Scheme 4 shows four reaction pathways starting from 2-boryl-1,3-diene 2f:\na) KHF₂/AcOH effects removal of Bpin to give the deborylated product 3 (yield 54%, 99∶1 Z∶E);\nb) Pd₂(dba)₃/SPhos-catalyzed Suzuki coupling with 4-iodobenzonitrile affords the arylated product 4 (yield 74%, >95∶5 Z∶E);\nc) H₂O₂/NaOH oxidation of the boronate gives the α,β,γ,δ-unsaturated ketone product 5 (yield 54%, >99∶1 E∶Z);\nd) nBuLi/CH₂Br₂ insertion followed by H₂O₂ oxidation provides the allylic alcohol product 6 (yield 40%, >99∶1 Z∶E).",
"Scheme 4 shows four reaction pathways starting from 2-boryl-1,3-diene 2f:\na) KHF₂/AcOH effects removal of Bpin to give the deborylated product 3 (yield 54%, >99∶1 Z∶E);\nb) Pd₂(dba)₃/SPhos-catalyzed Suzuki coupling with 4-iodobenzonitrile affords the arylated product 4 (yield 74%, >95∶5 Z∶E);\nc) H₂O₂/NaOH oxidation of the boronate gives the α,β,γ,δ-unsaturated ketone product 5 (yield 54%, >99∶1 E∶Z);\nd) nBuLi/CH₂Br₂ insertion followed by H₂O₂ oxidation provides the allylic alcohol product 6 (yield 40%, >99∶1 Z∶E).",
"Scheme 4 shows four reaction pathways starting from 2-boryl-1,3-diene 2f:\na) KHF₂/AcOH effects removal of Bpin to give the deborylated product 3 (yield 54%, >99∶1 Z∶E);\nb) Pd₂(dba)₃/SPhos-catalyzed Suzuki coupling with 4-iodobenzonitrile affords the arylated product 4 (yield 74%, >95∶5 Z∶E);\nc) H₂O₂/NaOH oxidation of the boronate gives the α,β,γ,δ-unsaturated ketone product 5 (yield 54%, >99∶1 E∶Z);\nd) nBuLi/CH₂Br₂ insertion followed by O₂ oxidation provides the allylic alcohol product 6 (yield 40%, >99∶1 Z∶E)."
] | 2
|
{
"title": "Chemo-, Regio-, and Stereoselective cis-Hydroboration of 1,3-Enynes: Copper-Catalyzed Access to (Z,Z)- and (Z,E)-2-Boryl-1,3-dienes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c01929",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c01929"
}
|
0
|
|
What are the main functional groups in product 4 obtained by the coupling in reaction b? What is its Z:E stereochemical selectivity?
|
[
"Product 4 contains: two para-methoxy-substituted phenyl rings; a contiguous 1,3-diene chain; a para-cyano (–C≡N) substituent. The product retains the Z configuration preference of the original diene, Z:E =95:5.",
"Product 4 contains: two para-methyl-substituted phenyl rings; a contiguous 1,3-diene chain; a para-cyano (–C≡N) substituent. The product retains the Z configuration preference of the original diene, Z:E >95:5.",
"Product 4 contains: two para-methoxy-substituted phenyl rings; a contiguous 1,3-diene chain; a para-cyano (–C≡N) substituent. The product retains the Z configuration preference of the original diene, Z:E >95:5.",
"Product 4 contains: one para-methoxy-substituted phenyl ring; a contiguous 1,3-diene chain; a para-phenol (–OH) substituent. The product retains the E configuration preference of the original diene, E:Z >95:5."
] | 2
|
{
"title": "Chemo-, Regio-, and Stereoselective cis-Hydroboration of 1,3-Enynes: Copper-Catalyzed Access to (Z,Z)- and (Z,E)-2-Boryl-1,3-dienes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c01929",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c01929"
}
|
0
|
|
What structural features does product 5 obtained in reaction c under H₂O₂/3 M NaOH conditions have? Please give the corresponding yield and E:Z ratio.
|
[
"Product 5 is an α,β,γ,δ-unsaturated ketone: the terminal of the diene backbone is oxidized to a carbonyl group (–C(=O)–), still retaining two para-methoxyphenyl rings. Yield 54%, stereoselectivity E:Z >99:1.",
"Product 5 is an α,β,γ,δ-unsaturated ketone: the terminal of the diene backbone is oxidized to a carbonyl group (–C(=O)–), still retaining two para-methoxyphenyl rings. Yield 54%, stereoselectivity Z:E >99:1.",
"Product 5 is an α,β,γ,δ-unsaturated ester: the terminal of the diene backbone is oxidized to a carbonyl group (–C(=O)–), still retaining two para-methoxyphenyl rings. Yield 54%, stereoselectivity E:Z >99:1.",
"Product 5 is an α,β,γ,δ-unsaturated ketone: the terminal of the diene backbone is oxidized to a carbonyl group (–C(=O)–), still retaining two para-methylphenyl rings. Yield 54%, stereoselectivity E:Z >99:1."
] | 0
|
{
"title": "Chemo-, Regio-, and Stereoselective cis-Hydroboration of 1,3-Enynes: Copper-Catalyzed Access to (Z,Z)- and (Z,E)-2-Boryl-1,3-dienes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c01929",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c01929"
}
|
0
|
|
Which compound's preparation requires transition metal catalysis?
|
[
"3",
"5",
"4",
"6"
] | 2
|
{
"title": "Chemo-, Regio-, and Stereoselective cis-Hydroboration of 1,3-Enynes: Copper-Catalyzed Access to (Z,Z)- and (Z,E)-2-Boryl-1,3-dienes",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c01929",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c01929"
}
|
3
|
|
How do different electron-donating/withdrawing substituents (such as OMe, NO2, CF3) affect the reaction yield?
|
[
"Experimental results show that electron-donating groups (such as OMe) and electron-withdrawing groups (such as Cl, Br) both give high yields (85–95%); whereas the strongly electron-withdrawing substituent NO2 significantly reduces the yield to 43%; CF3 substitution (electron-withdrawing) still has a good yield (93%).",
"Experimental results show that electron-donating groups (such as OMe) and the strongly electron-withdrawing group NO2 both give high yields (85–95%); only moderately withdrawing groups (such as CF3, Br) significantly reduce the yield to 43%; moreover, other halogen substituents also show similar moderate yields.",
"Experimental results show that the electron-donating group (such as OMe) gives the lowest yield (43%); whereas electron-withdrawing groups (such as Cl, Br, CF3, NO2) all give high yields (85–95%), and the effect of donating groups is more significant than that of withdrawing groups.",
"Experimental results show that all electron-withdrawing groups (such as Cl, Br, CF3, NO2) significantly increase the yield to 90–98%; whereas electron-donating groups (such as OMe) lead to a decreased yield of only 54%."
] | 0
|
{
"title": "Intramolecular Cobalt Porphyrin-Catalyzed Alkylation of 1-Isoindolinones by Site-Selective Insertion into a C(sp3)-H Bond",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02270",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02270"
}
|
3
|
|
In this reaction, what are the E-SMILES of the products corresponding to the bromo-substituted and chloro-substituted substrates?
|
[
"E-SMILES of product from bromo-substituted substrate (X=Br): Brc1cc2C(=O)N(CC2C1)CCC<sep><r>1:X</r>\nE-SMILES of product from chloro-substituted substrate (X=Cl): Clc1cc2C(=O)N(CC2C1)CCC<sep><r>1:X</r>",
"E-SMILES of product from bromo-substituted substrate (X=Br): Brc1cc2C(=O)N(CC2C1)CCO<sep><r>1:X</r>\nE-SMILES of product from chloro-substituted substrate (X=Cl): Clc1cc2C(=O)N(CC2C1)CCO<sep><r>1:X</r>",
"E-SMILES of product from bromo-substituted substrate (X=Br): Brc1cc2C(=O)N(CC2C1)CCC<sep><r>0:X</r>\nE-SMILES of product from chloro-substituted substrate (X=Cl): Clc1cc2C(=O)N(CC2C1)CCC<sep><r>0:X</r>",
"E-SMILES of product from bromo-substituted substrate (X=Br): Brc1cc2C(=O)N(CC2C1)CCC<sep><a>1:X</a>\nE-SMILES of product from chloro-substituted substrate (X=Cl): Clc1cc2C(=O)N(CC2C1)CCC<sep><a>1:X</a>"
] | 0
|
{
"title": "Intramolecular Cobalt Porphyrin-Catalyzed Alkylation of 1-Isoindolinones by Site-Selective Insertion into a C(sp3)-H Bond",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02270",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02270"
}
|
5
|
|
Please write out the reaction title and the overall description of the reaction for this scheme.
|
[
"The title of the scheme is \"Intramolecular, Cobalt(II) Porphyrin-Catalyzed Alkylation of 1-Isoindolinones Starting from Hydrazones\". Overall, this reaction uses hydrazone precursors of 1-isoindolinone derivatives and, under Co(TPP) catalysis, at 80 °C in CH2Cl2 solvent, with DBU and CuI as co-catalysts, generates radicals from the hydrazones which then insert into intramolecular C–H bonds to produce polycyclic nitrogen-containing heterocycles.",
"The title of the scheme is \"Intramolecular, Cobalt(II) Porphyrin-Catalyzed Alkylation of 1-Isoindolinones Starting from Hydrazones\". Overall, this reaction uses hydrazone (hydrazone) precursors of 1-isoindolinone derivatives and, under Co(TPP) (5,10,15,20-tetraphenyl-21H,23H-porphyrin cobalt(II)) catalysis, at 60 °C in o-dichlorobenzene solvent, in the presence of the strong base DBU, inserts the active methylene from the hydrazone into an intramolecular C–H bond to produce polycyclic nitrogen-containing heterocycles.",
"The title of the scheme is \"Intramolecular, Cobalt(II) Porphyrin-Catalyzed Arylation of 1-Isoindolinones Starting from Hydrazones\". Overall, this reaction uses hydrazone precursors of 1-isoindolinone derivatives and, under Co(TPP) catalysis, at 25 °C in MeCN solvent, using potassium carbonate (K2CO3) as the base, inserts the active methylene from the hydrazone into an intramolecular C–H bond to produce polycyclic nitrogen-containing heterocycles.",
"The title of the scheme is \"Intermolecular, Cobalt(II) Porphyrin-Catalyzed Alkylation of 1-Isoindolinones Starting from Hydrazones\". Overall, this reaction uses 1-isoindolinone derivatives and hydrazones which undergo cross-coupling under Co(TPP) catalysis, at 60 °C in o-dichlorobenzene solvent, using DBU as the base, to generate polycyclic nitrogen-containing heterocycles through bimolecular radical complementarity."
] | 1
|
{
"title": "Intramolecular Cobalt Porphyrin-Catalyzed Alkylation of 1-Isoindolinones by Site-Selective Insertion into a C(sp3)-H Bond",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02270",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02270"
}
|
0
|
|
What are the main reagents and conditions in the reaction, respectively?
|
[
"Substrate is the hydrazone (2a) derived from 1-isoindolinone; base is 2.5 equivalents of DBU; catalyst is 1 mol% Co(TPP); solvent is o-dichlorobenzene; reaction concentration is 20 mM; temperature 60 °C; reaction time 4 hours.",
"Substrate is the hydrazone (2a) derived from 1-isoindolinone; base is 2.5 equivalents of DBU; catalyst is 1 mol% Co(TPP); solvent is o-dichlorobenzene; reaction concentration is 20 mM; temperature 60 °C; reaction time 24 hours.",
"Substrate is the hydrazone (2a) derived from 1-isoindolinone; base is 2.5 equivalents of DBU; catalyst is 1 mol% Co(TPP); solvent is p-dichlorobenzene; reaction concentration is 20 mM; temperature 60 °C; reaction time 24 hours.",
"Substrate is the hydrazone (2a) derived from 1-isoindolinone; base is 2.5 equivalents of DBU; catalyst is 10 mol% Co(TPP); solvent is o-dichlorobenzene; reaction concentration is 20 mM; temperature 60 °C; reaction time 24 hours."
] | 1
|
{
"title": "Intramolecular Cobalt Porphyrin-Catalyzed Alkylation of 1-Isoindolinones by Site-Selective Insertion into a C(sp3)-H Bond",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02270",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02270"
}
|
0
|
|
Which product has the highest yield?
|
[
"1p has the highest yield, at 91%.",
"1r has the highest yield, at 99%.",
"1n has the highest yield, at 93%.",
"1t has the highest yield, at 94%."
] | 1
|
{
"title": "Intramolecular Cobalt Porphyrin-Catalyzed Alkylation of 1-Isoindolinones by Site-Selective Insertion into a C(sp3)-H Bond",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.4c02270",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.4c02270"
}
|
0
|
|
In this electrochemical coupling reaction, what electrochemical functions do the carbon anode and the iron cathode respectively perform?
|
[
"The carbon anode (anode) is mainly used to distribute current and does not directly participate in substrate transformation; the iron cathode (cathode) is responsible for both arene oxidation and proton reduction, thereby achieving the dehydrogenative coupling cycle.",
"The carbon anode (anode) is responsible for proton reduction to generate H2 gas; the iron cathode (cathode) is responsible for oxidizing the arene substrate, removing electrons to generate aryl radicals.",
"The carbon anode (anode) is responsible for oxidizing the azole substrate, removing electrons to generate azole radicals; the iron cathode (cathode) is responsible for proton reduction to generate H2 gas.",
"The carbon anode (anode) is responsible for oxidizing the arene substrate, removing electrons to generate aryl radicals; the iron cathode (cathode) is responsible for proton reduction to generate H2 gas, thereby completing the overall dehydrogenative coupling cycle."
] | 3
|
{
"title": "Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01409",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01409"
}
|
1
|
|
Please provide a Markush E-SMILES representation of a generic product, labeling the substituents R¹ and R² on the aromatic ring.
|
[
"*c1ccc(R1)c(-n2cccc2)c1<sep><a>0:R[2]</a><r>0:R[1]</r>",
"C1C=CC(N2C3C(=CC=CC=3)*=*2)=CC=1<sep><r>0:R[2]</r><r>2:R[1]</r><a>11:X</a><a>12:X</a>",
"*c1ccc(R1)c(-n2cccc2)c1<sep><a>1:R¹</a><r>0:R²</r>",
"*c1ccc(R1)c(-n2cccc2)c1<sep><a>0:R¹</a><r>1:R²</r>"
] | 1
|
{
"title": "Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01409",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01409"
}
|
5
|
|
Please write the English title of the electrochemical dehydrogenative C–N coupling reaction shown in the figure.
|
[
"Electrochemical Dehydrogenative C–N Coupling between Nitroarenes and Azoles in a Microflow Reactor.",
"Electrochemical Oxidative C–N Coupling between Azoles and Arenes in a Microflow Reactor.",
"Electrochemical Dehydrogenative C–O Coupling between Arenes and Azoles in a Microflow Reactor.",
"Electrochemical Dehydrogenative C–N Coupling between Arenes and Azoles in a Microflow Reactor."
] | 3
|
{
"title": "Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01409",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01409"
}
|
0
|
|
Regarding the reaction scheme of this electrochemical dehydrogenative C–N coupling, which of the following descriptions is correct?
|
[
"Using a substituted arene (Ar–H) and a nitrogen-containing heterocycle (Azole) as substrates, under conditions of room temperature, HFIP/CH₂Cl₂ (7∶3), Bu₄NPF₆ as supporting electrolyte, a flow electrochemical cell (carbon anode/iron cathode), current 20–30 mA, 10 min residence time, the substrate is oxidized at the anode to generate an aryl radical that couples with the heterocycle via C–N coupling to give an N-aryl heterocycle product, with H₂ gas as a byproduct.",
"Using a substituted arene (Ar–H) and a nitrogen-containing heterocycle (Azole) as substrates, under conditions of room temperature, HFIP/CH₂Cl₂ (7∶3), Bu₄NPF₆ as supporting electrolyte, a flow electrochemical cell (carbon anode/iron cathode), current 20–30 mA, 10 min residence time, the substrate is oxidized at the anode to generate an aryl radical that couples with the heterocycle via C–C coupling to give a biaryl product, with O₂ gas as a byproduct.",
"Using a substituted arene (Ar–H) and a nitrogen-containing heterocycle (Azole) as substrates, under conditions of room temperature, HFIP/CH₂Cl₂ (7∶3), Bu₄NPF₆ as supporting electrolyte, a flow electrochemical cell (platinum anode/iron cathode), current 20–30 mA, 10 min residence time, the substrate is oxidized at the anode to generate an aryl radical that couples with the heterocycle via C–N coupling to give an N-aryl heterocycle product, with H₂ gas as a byproduct.",
"Using a substituted arene (Ar–H) and a nitrogen-containing heterocycle (Azole) as substrates, under conditions of room temperature, HFIP/acetonitrile (7∶3), Bu₄NClO₄ as supporting electrolyte, a flow electrochemical cell (carbon anode/iron cathode), current 20–30 mA, 10 min residence time, the substrate is oxidized at the anode to generate an aryl radical that couples with the heterocycle via C–N coupling to give an N-aryl heterocycle product, with H₂ gas as a byproduct."
] | 0
|
{
"title": "Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01409",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01409"
}
|
2
|
|
Why do electron-donating-substituted arenes (such as 2,4,6-trimethylbenzene) give higher yields in this coupling reaction than electron-withdrawing-substituted arenes?
|
[
"Electron-donating substituents (such as methyl, tert-butyl) enhance adsorption of the substrate on the electrode surface, making electron transfer more efficient; whereas electron-withdrawing groups (such as CHO, CO2Me) reduce the substrate's affinity for the electrode, resulting in lower yields.",
"Electron-donating substituents (such as methyl, tert-butyl) stabilize the intermediates by forming hydrogen bonds with water molecules, reducing byproducts; whereas electron-withdrawing groups (such as CHO, CO2Me) cannot form such hydrogen bonds, leading to more byproducts and lower yields.",
"Electron-donating substituents (such as methyl, tert-butyl) increase the electron density of the aromatic ring, making it easier to be oxidized at the anode to form aryl radicals, which then couple with the heterocycle; whereas electron-withdrawing groups (such as CHO, CO2Me) decrease the aromatic ring's electron density, inhibiting anodic oxidation and resulting in lower yields.",
"Electron-donating substituents (such as methyl, tert-butyl) increase the substrate's solubility in HFIP/CH2Cl2, accelerating the overall reaction rate; but electron-withdrawing groups (such as CHO, CO2Me) decrease the substrate's solubility, so the yields are lower."
] | 2
|
{
"title": "Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor",
"journal": "JOURNAL OF ORGANIC CHEMISTRY",
"doi": "10.1021/acs.joc.1c01409",
"url": "https://pubs.acs.org/doi/10.1021/acs.joc.1c01409"
}
|
3
|
|
In 3a–3m, how do different anhydrides affect the yields? Explain the reasons using 3e (2-sulfobenzoic anhydride, 65%) and 3g (tetrafluoro-phthalic anhydride, 30%) as examples.
|
[
"Aryl lanthanide reagents act as nucleophiles; conjugated electron-withdrawing groups attached to the anhydride can better enhance the electrophilicity of the carbonyl carbon, promoting the cyclization reaction. In 2-sulfobenzoic anhydride, the electrophilicity of the carbonyl is enhanced due to the conjugated electron-withdrawing effect of the sulfonyl group, so the yield is higher; in tetrafluoro-phthalic anhydride, the F has both an electron-withdrawing inductive effect and an electron-donating conjugative effect, and in this reaction the conjugative effect outweighs the inductive effect, so the yield decreases significantly.",
"Aryl lanthanide reagents act as nucleophiles; conjugated electron-withdrawing groups on the anhydride can better enhance the electrophilicity of the carbonyl carbon, promoting cyclization. In 2-sulfobenzoic anhydride, the electrophilicity of the carbonyl is enhanced due to the conjugated electron-withdrawing effect of the sulfonyl group, so the yield is higher; in tetrafluoro-phthalic anhydride, the yield is reduced due to increased steric hindrance from too many substituents.",
"Aryl lanthanide reagents act as nucleophiles; conjugated electron-withdrawing groups on the anhydride can better enhance the electrophilicity of the carbonyl carbon, promoting cyclization. In 2-sulfobenzoic anhydride, the electrophilicity of the carbonyl is reduced due to the conjugated electron-withdrawing effect of the sulfonyl group, so the yield is higher; in tetrafluoro-phthalic anhydride, the F has both an electron-withdrawing inductive effect and an electron-donating conjugative effect, and in this reaction the conjugative effect outweighs the inductive effect, so the yield decreases significantly.",
"Aryl lanthanide reagents act as electrophiles; conjugated electron-withdrawing groups attached to the anhydride can better enhance the electrophilicity of the carbonyl carbon, promoting the cyclization reaction. In 2-sulfobenzoic anhydride, the electrophilicity of the carbonyl is enhanced due to the conjugated electron-withdrawing effect of the sulfonyl group, so the yield is higher; in tetrafluoro-phthalic anhydride, the F has both an electron-withdrawing inductive effect and an electron-donating conjugative effect, and in this reaction the conjugative effect outweighs the inductive effect, so the yield decreases significantly."
] | 0
|
{
"title": "Modular Synthetic Approach to Silicon-Rhodamine Homologues and Analogues via Bis-aryllanthanum Reagents",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c00512",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c00512"
}
|
3
|
|
Taking product 3b as an example, which anhydride does it originate from? What are the structural characteristics of the product?
|
[
"3b originates from the addition-cyclization reaction of diethyl maleate with an aryl lanthanum reagent; its product's core framework is two six-membered rings of 9,10-dihydroanthracene, one of the central carbons is substituted by dimethylsilyl, the other carbon forms a fused ring structure with diethyl maleate, and the phenyl rings on both sides each have a dimethylamino group at the position adjacent to the silyl group.",
"3b originates from the addition-cyclization reaction of dimethyl maleic anhydride with an aryl lanthanum reagent; its product's core framework is three six-membered rings of 9,10-dihydroanthracene, one of the central carbons is substituted by dimethylsilyl, the other carbon forms a spirocyclic structure with dimethyl maleic anhydride, and the phenyl rings on both sides each have a dimethylamino group at the meta position relative to the silyl group.",
"3b originates from the addition-cyclization reaction of phthalic anhydride with an aryl lanthanum reagent; its product's core framework is three six-membered rings of 9,10-dihydroanthracene, one of the central carbons is substituted by dimethylsilyl, the other carbon forms a spirocyclic structure with phthalic anhydride, and the phenyl rings on both sides each have a dimethylamino group at the para and ortho positions relative to the silyl substituent.",
"3b originates from the addition-cyclization reaction of tetrahydrophthalic anhydride with an aryl lanthanum reagent; its product's core framework is three six-membered rings of 10,11-dihydroanthracene, one of the central carbons is substituted by dimethylsilyl, the other carbon forms a spirocyclic structure with tetrahydrophthalic anhydride, and the phenyl rings on both sides each have a methylamino group at the meta position relative to the silyl group."
] | 1
|
{
"title": "Modular Synthetic Approach to Silicon-Rhodamine Homologues and Analogues via Bis-aryllanthanum Reagents",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c00512",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c00512"
}
|
0
|
|
What are the key steps and experimental conditions of this reaction?
|
[
"Step 1: In THF, add 4.2 equivalents of t-BuLi at -78 °C for metalation for 1 h; Step 2: at the same temperature add 2.2 equivalents of LaCl3·2LiCl and react for 30 min to generate the aryl lanthanum reagent; Step 3: add 1.5 equivalents of an anhydride or ester, warm from -78 °C to room temperature and react for 2–18 h to obtain the lactone product.",
"Step 1: In THF, add 4.2 equivalents of t-BuLi at -78 °C for metalation for 1 h; Step 2: at the same temperature add 2.2 equivalents of LaCl3·2LiCl and react for 30 min to generate the aryl lanthanum reagent; Step 3: add 1.5 equivalents of an anhydride or ester, warm from -78 °C to room temperature and react for 2–8 h to obtain the lactone product.",
"Step 1: In THF, add 4.2 equivalents of t-BuLi at -78 °C for metalation for 1 h; Step 2: at the same temperature add 2.2 equivalents of LaCl3·LiCl and react for 30 min to generate the aryl lanthanum reagent; Step 3: add 1.5 equivalents of an anhydride or ester, warm from -78 °C to room temperature and react for 2–18 h to obtain the lactone product.",
"Step 1: In THF, add 4.2 equivalents of t-BuLi at -78 °C for metalation for 1 h; Step 2: at room temperature add 2.2 equivalents of LaCl3·2LiCl and react for 30 min to generate the aryl lanthanum reagent; Step 3: add 1.5 equivalents of an anhydride or ester, warm from -78 °C to room temperature and react for 2–18 h to obtain the lactone product."
] | 0
|
{
"title": "Modular Synthetic Approach to Silicon-Rhodamine Homologues and Analogues via Bis-aryllanthanum Reagents",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c00512",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c00512"
}
|
2
|
|
What type of overall organic transformation is the reaction shown in Scheme 2a?
|
[
"The reaction first uses t-BuLi to desilylate aryl trimethylsilyl derivatives, then reacts with LaCl₃·2LiCl to generate aryl lanthanum reagents, and finally undergoes nucleophilic substitution with various anhydrides or esters to give multisubstituted aryl lactic acid products 3a–m.",
"The reaction first uses t-BuLi to metallate aryl bromides, then reacts with ZnCl₂ to generate aryl zinc reagents, and subsequently undergoes cross-coupling with various anhydrides or esters to give multisubstituted diaryl ketone products 3a–m.",
"The reaction first uses n-BuLi to metallate aryl bromides, then reacts with LaCl₃·2LiCl to generate aryl lanthanum reagents, and then undergoes nucleophilic addition-cyclization with various carbonates to give multisubstituted aryl lactone products 3a–m.",
"The reaction first uses t-BuLi to metallate aryl bromides, then reacts with LaCl₃·2LiCl to generate aryl lanthanum reagents, and finally undergoes nucleophilic addition-cyclization with various anhydrides or esters to give multisubstituted aryl lactone (pyranone) products 3a–m."
] | 3
|
{
"title": "Modular Synthetic Approach to Silicon-Rhodamine Homologues and Analogues via Bis-aryllanthanum Reagents",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c00512",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c00512"
}
|
2
|
|
Why should the aryllithium intermediate first be converted to an aryl-lanthanum reagent with LaCl₃·2LiCl, instead of directly reacting the aryllithium with the anhydride?
|
[
"Aryllithium reagents are too reactive, easily causing ring-opening, coupling, or side reactions with functional groups; whereas aryl-lanthanum reagents have better functional-group tolerance and controllable electrophilicity, which can improve the selectivity and yield of the desired addition−cyclization and reduce byproducts.",
"Aryllithium reagents are too reactive, easily causing ring-opening, coupling, or side reactions with functional groups; whereas aryl-lanthanum reagents have better functional-group tolerance and controllable nucleophilicity, which can improve the selectivity and yield of the desired addition−cyclization, and is unrelated to reducing byproduct formation.",
"Aryllithium reagents are too reactive, easily causing ring-opening, coupling, or side reactions with functional groups; whereas aryl-lanthanum reagents have better functional-group tolerance and controllable nucleophilicity, which can improve the selectivity and yield of the desired addition−cyclization and reduce byproducts.",
"LaCl₃·2LiCl mainly activates the anhydride by Lewis acid activation, enhancing its electrophilicity, thereby accelerating the addition−cyclization, and can improve the selectivity and yield of the desired addition−cyclization and reduce byproducts."
] | 2
|
{
"title": "Modular Synthetic Approach to Silicon-Rhodamine Homologues and Analogues via Bis-aryllanthanum Reagents",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.1c00512",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.1c00512"
}
|
1
|
|
Describe the reduction step from 6b to product 19, including reagents, solvents, and yield.
|
[
"Treat the hemiacetal 6b in THF/acetonitrile (mixed solvents) with excess NaBH4 at room temperature, fully reducing the aldehyde and ketone on the ring to give the 1,3-diol product 19, yield 75%.",
"Treat the hemiacetal 6b in THF/MeOH (mixed solvents) with excess NaBH4 at room temperature, fully reducing the aldehyde and ketone on the ring to give the 1,2-diol product 19, yield 75%.",
"Treat the hemiacetal 6b in THF/MeOH (mixed solvents) with an equivalent amount of NaBH4 at room temperature, fully reducing the aldehyde and ketone on the ring to give the 1,3-diol product 19, yield 75%.",
"Treat the hemiacetal 6b in THF/MeOH (mixed solvents) with excess NaBH4 at room temperature, fully reducing the aldehyde and ketone on the ring to give the 1,3-diol product 19, yield 75%."
] | 3
|
{
"title": "A Redox-Relay Heck Approach to Substituted Tetrahydrofurans",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c00769",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c00769"
}
|
2
|
|
In Scheme 3, what are the stereochemical features and enantiomeric ratio of the cyclic product 18 obtained by treating the allylsilane reagent with BF3·OEt2?
|
[
"Product 18 is a tetrahydrofuran bearing an exocyclic allyl and phenyl substituent; the allyl and phenyl are predominantly syn, and the obtained d.r. is 6.3:1.",
"Product 18 is a tetrahydrofuran bearing an exocyclic allyl and phenyl substituent; the allyl and phenyl are predominantly anti, but the actual d.r. is 1:12.6.",
"Product 18 is a tetrahydrofuran bearing an exocyclic allyl and methyl substituent; the allyl and methyl are predominantly anti, and the d.r. is 12.6:1.",
"Product 18 is a tetrahydrofuran bearing an exocyclic allyl and phenyl substituent; the allyl and phenyl are predominantly anti, and the obtained diastereomeric ratio (d.r.) is 12.6:1."
] | 3
|
{
"title": "A Redox-Relay Heck Approach to Substituted Tetrahydrofurans",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c00769",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c00769"
}
|
0
|
|
In the Pd(OAc)2/NaHCO3/TBAC system, when preparing 6b from 4 and 5b, what is the primary role of TBAC (tetrabutylammonium chloride) in the reaction?
|
[
"TBAC mainly acts as a ligand, stabilizing Pd(0) species through coordination and modulating the electron density at the metal center, thereby improving reaction selectivity and stereochemical control, rather than serving as a phase-transfer agent.",
"In this Pd-catalyzed carbon–carbon coupling system, TBAC primarily functions as a base, used to neutralize acidic byproducts generated during the reaction, thereby maintaining basic conditions in the reaction system and promoting the coupling reaction.",
"TBAC acts as a reductant in the reaction, reducing Pd(II) to the active Pd(0) catalyst, thereby accelerating oxidative addition and reductive elimination steps, but does not serve a phase-transfer role.",
"TBAC (tetrabutylammonium chloride) acts as a phase-transfer agent in this Pd-catalyzed carbon–carbon coupling and as a halide coordinating source; it can stabilize Pd intermediates and increase the solubility of the catalyst in polar solvents, thereby accelerating oxidative addition and reductive elimination and significantly improving the yield of 6b."
] | 3
|
{
"title": "A Redox-Relay Heck Approach to Substituted Tetrahydrofurans",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c00769",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c00769"
}
|
1
|
|
Please write out the title of Scheme 3 and the research object of that scheme.
|
[
"The title of Scheme 3 is \"Derivatization of Hemiacetal 19\", and the research object is compound 6b containing a chiral hemiacetal framework and its series of derivative products.",
"The title of Scheme 3 is \"Derivatization of Hemiacetal 6a\", and the research object is compound 6b containing a chiral hemiacetal framework and its series of derivative products.",
"The title of Scheme 3 is \"Derivatization of Hemiacetal 6b\", and the research object is compound 5b containing a chiral hemiacetal framework and its series of derivative products.",
"The title of Scheme 3 is \"Derivatization of Hemiacetal 6b\", and the research object is compound 6b containing a chiral hemiacetal framework and its series of derivative products."
] | 3
|
{
"title": "A Redox-Relay Heck Approach to Substituted Tetrahydrofurans",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c00769",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c00769"
}
|
0
|
|
What is the yield of the preparation of 6b?
|
[
"83%",
"72%",
"98%",
"77%"
] | 2
|
{
"title": "A Redox-Relay Heck Approach to Substituted Tetrahydrofurans",
"journal": "ORGANIC LETTERS",
"doi": "10.1021/acs.orglett.3c00769",
"url": "https://pubs.acs.org/doi/10.1021/acs.orglett.3c00769"
}
|
0
|
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