Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(34), P. 18753 - 18759

Published: Aug. 15, 2023

The asymmetric difunctionalization of alkenes, a method transforming readily accessible alkenes into enantioenriched chiral structures high value, has long been focal point organic synthesis. Despite tremendous efforts in this domain, it remains considerable challenge to devise enantioselective oxidative dicarbofunctionalization even though these transformations can utilize stable and unfunctionalized functional group donors. In context, we report herein photoelectrocatalytic for the heteroarylcyanation aryl which employs heteroarenes through C-H functionalization. photoelectrochemical catalysis (PEAC) combines photoredox electrocatalysis facilitate formation two C-C bonds operating via hydrogen (H2) evolution obviating need external chemical oxidants.

Language: Английский

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Recent Advances in Reactions Involving Carbon Dioxide Radical Anion

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 15991 - 16011

Published: Nov. 28, 2023

Carbon dioxide radical anion (CO2•–) is a highly reactive nucleophilic species that has recently emerged in organic chemistry as strong single electron donor (reductant) and reactant for the synthesis of carboxylic acids. In general, CO2•– can be generated by either direct reduction CO2 or HAT formate salts. Achievements reactions involving have been witnessed recent years. This Review summarizes advances highlighting some challenges identifying potential areas improvement, which may offer inspiration future studies.

Language: Английский

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Photoelectrocatalytic C–H amination of arenes

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 7959 - 7962

Published: Jan. 1, 2023

Reported herein is an organocatalyzed photoelectrochemical C(aryl)–H amination reaction for direct access to anilides from easily available and stable arenes carbamates without the need sacrificial oxidants.

Language: Английский

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Photoredox streamlines electrocatalysis: photoelectrosynthesis of polycyclic pyrimidin-4-ones through carbocyclization of unactivated alkenes with malonates

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(7), P. 4199 - 4208

Published: Jan. 1, 2024

A new photoelectrocatalytic mode permits the synthesis of polycyclic pyrimidin-4-ones through dehydrogenative cyclization malonates with unactivated alkenes.

Language: Английский

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Visible-light-driven alkene dicarboxylation with formate and CO₂ under mild conditions

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 6178 - 6183

Published: Jan. 1, 2024

Low-cost formate salt was used as the reductant and part of carboxyl source in a visible-light-driven dicarboxylation diverse alkenes, including simple styrenes. The highly competing hydrocarboxylation side reaction successfully overridden. Good yields products were obtained under mild conditions at ambient temperature pressure CO

Language: Английский

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Electroreductive Remote Benzylic C(sp³)–H Arylation of Aliphatic Ethers Using Cyanoarenes for the Synthesis of α-(Hetero)aryl Ethers

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2440 - 2444

Published: March 19, 2024

An iodoarene-driven electroreductive remote C(sp3)–H arylation of unsymmetrical 1-(o-iodoaryl)alkyl ethers with cyanoarenes for the site selective synthesis α-(hetero)aryl is developed. With introduction as both aryl sources and electron transfer mediators, this method includes an strategy to enable regiocontrollable formation two new bonds, one C(sp2)–H bond, C(sp2)–C(sp3) in a single reaction step through sequence halogen atom (XAT), hydrogen (HAT), radical–radical coupling, decyanation.

Language: Английский

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Self‐ or Acridinium‐Catalyzed Electrophotosynthesis of Thiocyanato Heterocycles from Activated Alkenes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(10), P. 2352 - 2362

Published: April 5, 2024

Abstract While the emergence of electrophotochemistry provides opportunities, such a chemistry at this stage suffers from limited reaction types and high photocatalyst loadings. A self‐catalyzed electrophotosynthesis as well one with low loading is presented. These external‐oxidant‐free cyclizations are enabling applicable to range activated alkenes, affording diverse array thiocyanato heterocycles including 4‐pyrrolin‐2‐ones, isoquinoline‐1,3‐diones, indolo[2,1‐ ]isoquinolin‐6(5 H )‐ones, benzoimidazo[2,1‐ )‐ones indolin‐2‐ones, protocols amenable late‐stage diversification complex molecular architectures gram‐scale syntheses. Sunlight could serve light source, be conducted in an all‐solar‐driven mode using commercially available photovoltaic panel produce electricity.

Language: Английский

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Electrophotocatalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(21), P. 12264 - 12304

Published: Oct. 23, 2024

Electrocatalysis and photocatalysis have been the focus of extensive research efforts in organic synthesis recent decades, these powerful strategies provided a wealth new methods to construct complex molecules. Despite intense efforts, only recently has there significant on combined use two modalities. Nevertheless, past five years witnessed rapidly growing interest area electrophotocatalysis. This hybrid strategy capitalizes enormous benefits using photons as reagents while also employing an electric potential convenient tunable source or sink electrons. Research this topic led number for C-H functionalization, reductive cross-coupling, olefin addition among others. field seen broad range catalyst types, including both metal organocatalysts. Of particular note work with open-shell photocatalysts, which tend comparatively large redox potentials. Electrochemistry provides means generate such species, making electrophotocatalysis particularly amenable intriguing class catalyst. review surveys applied synthesis, organized broadly into oxidative, reductive, neutral transformations.

Language: Английский

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Electro-reductive carboxylation of C Cl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO2

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 110104 - 110104

Published: June 8, 2024

Language: Английский

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Electroreduction strategy: a sustainable tool for the generation of aryl radicals

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4318 - 4342

Published: Jan. 1, 2024

This review primarily focuses on the generation of aryl radicals via an electroreduction strategy, and systematically elaborates synthetic applications, scope, limitations substrates.

Language: Английский

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