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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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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The Strategies towards Electrochemical Generation of Aryl Radicals

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 16, 2024

The advancement in electrochemical techniques has unlocked a new path for achieving unprecedented oxidations and reductions of aryl radical precursors controlled selective manner. This approach facilitates the construction aromatic carbon-carbon carbon-heteroatom bonds. In light green merits growing importance this technique chemistry, review aims to provide an overview recent advance generation radicals organized by precursor type, with focus on substrate scope, limitation, underlying mechanism, thereby inspiring future work generation.

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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Electrochemical Difunctionalization of Alkenes

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Abstract Owing to their wide utilizations in synthesis and products prevalence numerous natural products, pharmaceuticals functional materials, the alkene difunctionalization methods for selective transformations of olefins are important have attracted much attention form synthetic chemists. Among them, electrochemical reaction is particularly promising has becoming a potent sustainable tool alkenes into vicinal difunctionalized structures organic through simultaneous incorporation two groups. Herein, we summarize recent progress reactions according types as well category radicals over past five years. By selecting remarkable examples, elaborately discussed substrate scope mechanisms olefin reaction.

Language: Английский

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Throwing Light on Synthetic Molecular Photoelectrocatalysis (Part I): coupling both techniques and results interpretation

Current Opinion in Electrochemistry, Journal Year: 2025, Volume and Issue: unknown, P. 101673 - 101673

Published: Feb. 1, 2025

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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