Molecular Photoelectrocatalysis for Radical Reactions DOI
Peng Xiong, Hai‐Chao Xu

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

Photocatalytic Late-Stage C–H Functionalization DOI
Peter Bellotti, Huan‐Ming Huang,

Teresa Faber

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

Citations

322
Electrochemical Late-Stage Functionalization DOI Creative Commons
Yulei Wang, Suman Dana, Hao Long

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

Citations

141
Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation DOI
Xiao‐Li Lai, Ming Chen, Yuqi Wang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20201 - 20206

Published: Oct. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Language: Английский

Citations

97
Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions DOI
Yaowen Liu, Pengfei Li, Yanwei Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: June 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Language: Английский

Citations

85
Photoinduced copper-catalyzed enantioselective coupling reactions DOI
Liangliang Song, Lingchao Cai, Lei Gong

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(7), P. 2358 - 2376

Published: Jan. 1, 2023

This review highlights the progress in photoinduced copper-catalyzed enantioselective coupling reactions.

Language: Английский

Citations

66
Organoelectrophotocatalytic C–H Silylation of Heteroarenes DOI

Qinhui Wan,

Zhong‐Wei Hou,

Xin‐Ru Zhao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(6), P. 1008 - 1013

Published: Feb. 3, 2023

An organoelectrophotocatalytic approach for the C-H silylation of heteroarenes through dehydrogenation cross-coupling with H2 evolution has been developed. The strategy is carried out under a simple and efficient monocatalytic system by employing 9,10-phenanthrenequinone both as an organocatalyst hydrogen atom transfer (HAT) reagent, which avoids need external HAT oxidant, or metal reagent. A variety can be compatible in satisfactory yields excellent regioselectivity.

Language: Английский

Citations

64
Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization DOI
Xiao‐Li Lai, Hai‐Chao Xu

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

Citations

63
Redox mediator-stabilized wide-bandgap perovskites for monolithic perovskite-organic tandem solar cells DOI
Shengfan Wu, Yichao Yan, Jun Yin

et al.

Nature Energy, Journal Year: 2024, Volume and Issue: 9(4), P. 411 - 421

Published: Jan. 26, 2024

Language: Английский

Citations

60
Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis DOI Creative Commons
Xiaomin Shu,

De Zhong,

Qian Huang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 9, 2023

Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.

Language: Английский

Citations

56
Organoelectrophotocatalytic Generation of Acyl Radicals from Formamides and Aldehydes: Access to Acylated 3-CF3-2-Oxindoles DOI
Hong He,

Qinhui Wan,

Zhong‐Wei Hou

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(38), P. 7014 - 7019

Published: Sept. 18, 2023

Organoelectrophotocatalytic generation of acyl radicals from formamides and aldehydes to synthesize acylated 3-CF3-2-oxindoles has been developed. This protocol features a monocatalytic system using 9,10-phenanthrenequinone (PQ) both as catalyst hydrogen atom transfer (HAT) reagent, which avoids the use an external HAT metal oxidant. A variety have obtained in satisfactory yields CF3-substituted N-arylacrylamides via tandem radical cyclization.

Language: Английский

Citations

49