Electrochemical Late-Stage Functionalization

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

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Photoinduced copper-catalyzed enantioselective coupling reactions

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

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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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A tutorial on asymmetric electrocatalysis

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(23), P. 8106 - 8125

Published: Jan. 1, 2023

This tutorial review delves into the unique advantages of electrochemistry in context asymmetric catalysis, first providing a brief introduction to electrosynthesis, then exploring representative case studies with mechanistic focus.

Language: Английский

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Anaerobic Hydroxylation of C(sp³)–H Bonds Enabled by the Synergistic Nature of Photoexcited Nitroarenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 2794 - 2799

Published: Jan. 25, 2023

A photoexcited-nitroarene-mediated anaerobic C-H hydroxylation of aliphatic systems is reported. The success this reaction due to the bifunctional nature photoexcited nitroarene, which serves as bond activator and oxygen atom source. Compared previous methods, approach cost- atom-economical commercial availability sole mediator reaction. Because conditions transformation, a noteworthy expansion in substrate scope can be obtained compared prior reports. Mechanistic studies support that nitroarenes engage successive hydrogen transfer radical recombination events with hydrocarbons, leading N-arylhydroxylamine ether intermediates. Spontaneous fragmentation these intermediates leads key products.

Language: Английский

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Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp³)/Si–H Functionalization and Hydrofunctionalization of Alkenes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8731 - 8751

Published: June 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Language: Английский

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Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp³)−H Alkenylation**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Language: Английский

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Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Aug. 22, 2023

Abstract Organic electrosynthesis has consistently aroused significant interest within both academic and industrial spheres. Despite the considerable progress achieved in this field, majority of electrochemical transformations have been conducted through utilization direct‐current (DC) electricity. In contrast, application alternating current (AC), characterized by its polarity‐alternating nature, remains infancy sphere organic synthesis, primarily due to absence a comprehensive theoretical framework. This minireview offers an overview recent advancements AC‐driven seeks elucidate differences between DC AC electrolytic methodologies probing into their underlying physical principles. These encompass ability preclude deposition metal catalysts, precision modulating oxidation reduction intensities, mitigation mass transfer processes.

Language: Английский

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Enantioselective Cyanofunctionalization of Aromatic Alkenes via Radical Anions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1410 - 1422

Published: Jan. 5, 2024

Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis valuable compounds because they have both unpaired spins charge. However, relatively few synthetic applications alkene anions emerged due to a dearth generally applicable mild anion generation approaches. Precise control over chemo- stereoselectivity in anion-mediated processes represents another long-standing challenge their high reactivity. To overcome these issues, here, we develop new redox-neutral strategy that seamlessly merges photoredox copper catalysis enable controlled orthogonal enantioselective cyanofunctionalization via distonic-like species. This enables highly regio-, chemo-, hydrocyanation, deuterocyanation, cyanocarboxylation alkenes without stoichiometric reductants or oxidants under visible light irradiation. protocol provides blueprint exploration transformation potential anions.

Language: Английский

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Photocatalyzed Enantioselective Functionalization of C(sp³)–H Bonds

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1209 - 1223

Published: Jan. 3, 2024

Owing to its diverse activation processes including single-electron transfer (SET) and hydrogen-atom (HAT), visible-light photocatalysis has emerged as a sustainable efficient platform for organic synthesis. These provide powerful avenue the direct functionalization of C(sp3)–H bonds under mild conditions. Over past decade, there have been remarkable advances in enantioselective bond via combined with conventional asymmetric catalysis. Herein, we summarize involving discuss two main pathways this emerging field: (a) SET-driven carbocation intermediates are followed by stereospecific nucleophile attacks; (b) photodriven alkyl radical further enantioselectively captured (i) chiral π-SOMOphile reagents, (ii) stereoselective transition-metal complexes, (iii) another distinct stereoscopic species. We aim key reaction design, catalyst development, mechanistic understanding, new insights into rapidly evolving area research.

Language: Английский

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