Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis DOI
Akira Matsumoto, Natsumi Maeda, Keiji Maruoka

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20344 - 20354

Published: July 25, 2023

Organic molecules that can be connected to multiple substrates by sequential C-C bond formations utilized as linchpins in multicomponent processes. While they are useful for rapidly increasing molecular complexity, most of the reported linchpin coupling methods rely on use organometallic species strong carbon nucleophiles form bonds, which narrows functional group compatibility. Here, we describe a metal-free, radical-mediated approach using formyl-stabilized phosphonium ylide multifunctional under visible-light photoredox conditions. The present method uses ambiphilic character ylide, serves both nucleophilic and an electrophilic carbon-centered radical source. stepwise controllable generation these intermediates allows photocatalysis involving two mechanistically distinct additions, initiated same photocatalyst one pot with high tolerance. methodology enables bidirectional assembly electronically differentiated alkene fragments thus offers rapid modular access 1,4-dicarbonyl compounds versatile synthetic intermediates.

Language: Английский

A versatile catalyst-free redox system mediated by carbon dioxide radical and dimsyl anions DOI Creative Commons
Yan Huang, Qian Zhang,

Li−Li Hua

et al.

Cell Reports Physical Science, Journal Year: 2022, Volume and Issue: 3(8), P. 100994 - 100994

Published: Aug. 1, 2022

The development of new, efficient ways to initiate redox events has long been a goal in organic synthesis. A system mediated by carbon dioxide radical and dimsyl anions is demonstrated variety transformations, including hydrocarboxylation, hydroxycarboxylation, Birch reduction, three-component reductive coupling carbonyl compounds, amines, cyanopyridines, are achieved catalyst-free fashion using this method, giving valuable acids, saturated skeletons, α-pyridyl amines high efficiency. This strategy promises wide applications other types reactions complements current photoredox catalysis methodologies.

Language: Английский

Citations

27
Catalytic Carbon Dioxide Fixation Reactions Based on Transition Metal Complexes and Their Systems DOI
Nobuharu Iwasawa

Bulletin of the Chemical Society of Japan, Journal Year: 2023, Volume and Issue: 96(8), P. 824 - 841

Published: July 21, 2023

Abstract In this Account, transition metal-catalyzed carboxylation reactions developed in our laboratory are summarized according to the type of reaction. Design new metal catalysts or catalyst systems is essential part study and emphasis placed on mechanistic aspects newly reactions, which have attracted interest research.

Language: Английский

Citations

15
Catalyst-free defluorinative alkylation of trifluoromethyls DOI
Yan Huang,

Yuan-Cui Wan,

Yu Shao

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 8280 - 8285

Published: Jan. 1, 2023

A visible-light induced catalyst-free strategy was developed for the defluorinative alkylation of trifluoromethyls via CO 2 ˙ − . Various trifluoromethyl derivatives and alkenes could participate in reaction smoothly.

Language: Английский

Citations

14
CO2 Radical Anion in Photochemical Dicarboxylation of Alkenes DOI

Sai Wang,

Pei Xu, Xu Zhu

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(17)

Published: June 25, 2023

Abstract CO 2 radical anion (CO ⋅ − ) is a highly reductive species ( E red =−2.2 V vs SCE), which can undergo Giese addition to an unsaturated C−C bond and install carbonyl group synthesize acids. Normally, it has been generated through the direct reduction of gas or from formate salts via HAT (hydrogen atom transfer) as BDE (bond dissociation energy) C−H in only around 86 kcal/mol. This concept highlights recent developments on alkenes dicarboxylation reaction with and/or sources. In these reactions, played significant roles carboxylation step.

Language: Английский

Citations

13
Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis DOI
Akira Matsumoto, Natsumi Maeda, Keiji Maruoka

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20344 - 20354

Published: July 25, 2023

Organic molecules that can be connected to multiple substrates by sequential C-C bond formations utilized as linchpins in multicomponent processes. While they are useful for rapidly increasing molecular complexity, most of the reported linchpin coupling methods rely on use organometallic species strong carbon nucleophiles form bonds, which narrows functional group compatibility. Here, we describe a metal-free, radical-mediated approach using formyl-stabilized phosphonium ylide multifunctional under visible-light photoredox conditions. The present method uses ambiphilic character ylide, serves both nucleophilic and an electrophilic carbon-centered radical source. stepwise controllable generation these intermediates allows photocatalysis involving two mechanistically distinct additions, initiated same photocatalyst one pot with high tolerance. methodology enables bidirectional assembly electronically differentiated alkene fragments thus offers rapid modular access 1,4-dicarbonyl compounds versatile synthetic intermediates.

Language: Английский

Citations

13