Transition metal catalysis is one of the most important tools to construct carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. Visible-light photoredox catalysis has recently drawn considerable atte...Transition metal catalysis is one of the most important tools to construct carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. Visible-light photoredox catalysis has recently drawn considerable attention of the scientific community owing to its unique activation modes and significance for the green synthesis. The merger of photoredox catalysis with transition metal catalysts, termed metallaphotoredox catalysis, has become a popular strategy for expanding the synthetic utility of visiblelight photocatalysis. This strategy has led to the discovery of novel asymmetric transformations, which are unfeasible or not easily accessible by a single catalytic system. This contemporary area of organic chemistry holds promise for the development of economical and environmentally friendly methods for the asymmetric synthesis of chiral compounds. In this review, the advances in the enantioselective metallaphotoredox catalysis(EMPC) are summarized.展开更多
This review summarizes the recent advances in the catalytic syntheses of CFS-containing organic molecules using various nucleophilic or electrophilic trifluoromethylthiolating reagents.C-halogen and C—H bonds in vari...This review summarizes the recent advances in the catalytic syntheses of CFS-containing organic molecules using various nucleophilic or electrophilic trifluoromethylthiolating reagents.C-halogen and C—H bonds in various molecules have been transformed to C—SCFbonds by transition-metal-catalyzed reactions,such as cross-coupling of aryl halides.Enantioselective reactions controlled by chiral metal complexes or chiral organocatalysts have afforded many trifluoromethylthiolated chiral architectures,such as β-ketoesters and oxindoles.Very recently,visible-light-induced photoredox trifluoromethylthiolations have been developed,providing versatile CFS-containing structures efficiently.展开更多
Racemicα-chloro imidazol-2-yl-ketones undergo an enantioconvergent photoactivated C–C bond formation with N-aryl glycines catalyzed by a single bis-cyclometalated chiral-at-rhodium catalyst in yields of up to 80%and...Racemicα-chloro imidazol-2-yl-ketones undergo an enantioconvergent photoactivated C–C bond formation with N-aryl glycines catalyzed by a single bis-cyclometalated chiral-at-rhodium catalyst in yields of up to 80%and up to 98%enantiomeric excess(ee).Control experiments support a mechanism which is initiated by a single electron transfer from N-aryl glycinate to the photochemically excited rhodium-boundα-chloro imidazol-2-yl-ketone,followed by chloride fragmentation of theα-chloroketone,decarboxylation of the glycinate,and a subsequent highly stereocontrolled radical-radical coupling.This work showcases the ability of the chiral rhodium catalyst to serve a dual function as chiral Lewis acid and at the same time as the photoredox active species upon substrate binding.展开更多
基金supported by the National Key Research and Development Program of China(No.2021YFA1500703 to Ganglong Cui)Distinguished Professorship of Chang Jiang Scholars of Ministry of Education of China(Ganglong Cui)+1 种基金the Fundamental Research Funds for the Central Universitiesthe National Natural Science Foundation of China(No.22233001 to Ganglong Cui,No.22003043 to Xiang-Yang Liu)。
基金supported by the National Natural Science Foundation of China(21971110,21732003)。
文摘Transition metal catalysis is one of the most important tools to construct carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. Visible-light photoredox catalysis has recently drawn considerable attention of the scientific community owing to its unique activation modes and significance for the green synthesis. The merger of photoredox catalysis with transition metal catalysts, termed metallaphotoredox catalysis, has become a popular strategy for expanding the synthetic utility of visiblelight photocatalysis. This strategy has led to the discovery of novel asymmetric transformations, which are unfeasible or not easily accessible by a single catalytic system. This contemporary area of organic chemistry holds promise for the development of economical and environmentally friendly methods for the asymmetric synthesis of chiral compounds. In this review, the advances in the enantioselective metallaphotoredox catalysis(EMPC) are summarized.
基金Support of our work by National Basic Research Program of China(973 Program,No.2012CB821600)National Natural Science Foundation of China(Nos.21421002,21172241,21302207,21672239)
文摘This review summarizes the recent advances in the catalytic syntheses of CFS-containing organic molecules using various nucleophilic or electrophilic trifluoromethylthiolating reagents.C-halogen and C—H bonds in various molecules have been transformed to C—SCFbonds by transition-metal-catalyzed reactions,such as cross-coupling of aryl halides.Enantioselective reactions controlled by chiral metal complexes or chiral organocatalysts have afforded many trifluoromethylthiolated chiral architectures,such as β-ketoesters and oxindoles.Very recently,visible-light-induced photoredox trifluoromethylthiolations have been developed,providing versatile CFS-containing structures efficiently.
基金supported by the Deutsche Forschungsgemeinschaft(ME 1805/17-1)
文摘Racemicα-chloro imidazol-2-yl-ketones undergo an enantioconvergent photoactivated C–C bond formation with N-aryl glycines catalyzed by a single bis-cyclometalated chiral-at-rhodium catalyst in yields of up to 80%and up to 98%enantiomeric excess(ee).Control experiments support a mechanism which is initiated by a single electron transfer from N-aryl glycinate to the photochemically excited rhodium-boundα-chloro imidazol-2-yl-ketone,followed by chloride fragmentation of theα-chloroketone,decarboxylation of the glycinate,and a subsequent highly stereocontrolled radical-radical coupling.This work showcases the ability of the chiral rhodium catalyst to serve a dual function as chiral Lewis acid and at the same time as the photoredox active species upon substrate binding.
