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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Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

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Dual-Catalyzed Stereodivergent Electrooxidative Homocoupling of Benzoxazolyl Acetate

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1522 - 1531

Published: Jan. 3, 2024

The development of a reliable strategy for stereodivergent radical reactions that allows convenient access to all stereoisomers homocoupling adducts with multiple stereogenic centers remains an unmet goal in organic synthesis. Herein, we describe dual-catalyzed electrooxidative C(sp3)–H/C(sp3)–H complete absolute and relative stereocontrol the synthesis molecules contiguous quaternary stereocenters general predictable manner. reaction is achieved by synergistically utilizing two distinct chiral catalysts convert identical racemic substrates into inherently distinctive reactive intermediates, dictate enantioselective addition, allow full complement stereoisomeric products via simple catalyst permutation. successful execution dual-electrocatalytic programmed activation provides significant conceptual advantage will serve as useful foundation further research cooperative stereocontrolled transformations diversity-oriented

Language: Английский

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Electrochemical generation and utilization of radical intermediates

Current Opinion in Electrochemistry, Journal Year: 2024, Volume and Issue: 44, P. 101447 - 101447

Published: Jan. 26, 2024

Language: Английский

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Molecular Photoelectrocatalysis for Radical Reactions

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes capacity to offer novel reactivity selectivity, represents an emerging field in chemistry that addresses growing demands for environmental sustainability synthetic efficiency. This synergistic approach permits access a wider range redox potentials, facilitates transformations under gentler electrode decreases use external harsh reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we others reported first examples modern molecular photoelectrocatalysis. These studies showcased immense hybrid strategy, only inherits strengths its parent fields but also unlocks unprecedented enabling challenging mild conditions while minimizing reliance on stoichiometric oxidants or reductants.In Account, present our efforts develop photoelectrocatalytic strategies leverage homogeneous catalysts facilitate diverse radical reactions. By integrating electrocatalysis with key photoinduced processes such as single electron transfer (SET), ligand-to-metal charge (LMCT), hydrogen atom (HAT), have established methods transform substrates organotrifluoroborates, arenes, carboxylic acids, alkanes into reactive intermediates. intermediates subsequently engage heteroarene C-H functionalization Importantly, photoelectrochemical catalysts, generated bulk solution readily participate efficient reactions without undergoing further overoxidation carbocations, common challenge conventional electrochemical systems.By integration photoelectrocatalysis asymmetric catalysis, developed catalysis (PEAC), proves be enantioselective synthesis chiral nitriles. involves two relay catalytic cycles: initial process engenders benzylic radicals from precursors alkyl aryl alkenes, C-radicals are then subjected cyanation subsequent copper-electrocatalytic cycle.Within realm oxidative transformations, anode serves crucial component recycling generating photocatalyst, cathode promotes proton reduction. dual functionality enables via H

Language: Английский

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Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4024 - 4040

Published: Jan. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

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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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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Enantioselective Decarboxylative Hydrogen-Atom Transfer Reaction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Direct enantioselective decarboxylative transformations of carboxylic acids have become powerful tools for constructing structurally and functionally diverse molecules. Herein, an unprecedented organocatalyzed protocol enantioconvergent reduction was established by leveraging dual catalysis photoredox-mediated radical generation a thiol-catalyzed asymmetric hydrogen-atom transfer process. With this hydrodecarboxylation, variety chiral 3-substituted indolines were attained from the in moderate to excellent yields with high enantioselectivities.

Language: Английский

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Asymmetric Paired Electrocatalysis: Enantioselective Olefin–Sulfonylimine Coupling

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(3), P. 1984 - 1991

Published: Dec. 19, 2023

Asymmetric electrocatalysis offers exciting new strategies for the synthesis of chiral molecules through novel reaction pathways. However, simultaneous activation reactants on both electrodes via asymmetric paired electrolysis, which is more energy efficient and economic than single half-electrode synthesis, remains a formidable challenge. Herein, an olefin–sulfonylimine coupling presented first time. In this protocol, Co-catalyzed hydrogen atom transfer anode Ni-catalyzed sulfonylimine reduction cathode were seamlessly cross-coupled. The catalytic system enables formation amine products bearing tetrasubstituted carbon stereocenter with high enantioselectivity (up to 96% ee).

Language: Английский

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