General electrochemical Minisci alkylation of N-heteroarenes with alkyl halides DOI Creative Commons
Roberto del Río‐Rodríguez,

Lorena Fragoso-Jarillo,

Alberto F. Garrido‐Castro

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(22), P. 6512 - 6518

Published: Jan. 1, 2022

Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of

Language: Английский

Electrocatalysis as an enabling technology for organic synthesis DOI
Luiz F. T. Novaes, Jinjian Liu, Yifan Shen

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Language: Английский

Citations

872

Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis DOI
Nicholas E. S. Tay, Dan Lehnherr, Tomislav Rovis

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

Citations

357

Electrochemical Oxidation Induced Selective C–C Bond Cleavage DOI
Shi‐Hui Shi, Yujie Liang, Ning Jiao

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 485 - 505

Published: Oct. 5, 2020

Selective C–C bond cleavage under mild conditions can serve as a valuable tool for organic syntheses and macromolecular degradation. However, the conventional chemical methods have largely involved use of noble transition-metal catalysts well stoichiometric perhaps environmentally unfriendly oxidants, compromising overall sustainable nature transformation chemistry. In this regard, electrochemical has been identified scalable strategy that employs electricity to replace byproduct-generating reagents. To date, progress made in area mainly relied on Kolbe electrolysis related processes. Encouragingly, more examples bonds via other maneuvers recently developed. This review provides an overview most recent significant developments electrochemically oxidative selective cleavage, with emphasis both synthetic outcomes reaction mechanisms, it showcases innate advantages exciting potentials synthesis.

Language: Английский

Citations

352

Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts DOI
Cong Ma, Ping Fang,

Zhao‐Ran Liu

et al.

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

Citations

293

Carbon dioxide cycle via electrocatalysis: Electrochemical carboxylation of CO2 and decarboxylative functionalization of carboxylic acids DOI Creative Commons
Zixin Yang, Yi Yu,

Liangchuan Lai

et al.

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(1), P. 19 - 26

Published: Feb. 1, 2021

As one of the most important biogeochemical cycles, carbon dioxide (CO2) cycle between atmosphere and biosphere has a profound impact on life earth. Therefore, search for sustainable solutions to normalize currently unbalanced is central research topic many scientific disciplines. The green electrocatalysis offers very promising answer cycle. In this review, recent advances in enabled CO2 including electrochemical carboxylation decarboxylative functionalization carboxylic acids are highlighted.

Language: Английский

Citations

120

Electrochemical Nozaki–Hiyama–Kishi Coupling: Scope, Applications, and Mechanism DOI
Yang Gao, David E. Hill, Wei Hao

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(25), P. 9478 - 9488

Published: June 15, 2021

One of the most oft-employed methods for C–C bond formation involving coupling vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki–Hiyama–Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to feasibility such a process, those precedents were never applied others due cumbersome setups limited scope. Here we show that carefully optimized procedure can enable sustainable approach NHK, even in asymmetric fashion on highly complex medicinally relevant systems. The e-NHK non-canonical substrate classes, as redox-active esters, participate low loadings when conventional chemical techniques fail. A combination detailed kinetics, cyclic voltammetry, situ UV–vis spectroelectrochemistry these processes illuminates subtle features this mechanistically intricate process.

Language: Английский

Citations

111

Organophotoelectrocatalytic C(sp2)–H alkylation of heteroarenes with unactivated C(sp3)–H compounds DOI

Qinhui Wan,

Xia-Die Wu,

Zhong-Wei Hou

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(42), P. 5502 - 5505

Published: Jan. 1, 2024

An organophotoelectrocatalytic method for the C(sp 2 )–H alkylation of heteroarenes with unactivated 3 compounds via dehydrogenation cross-coupling was developed.

Language: Английский

Citations

28

Aryl acyl peroxides for visible-light induced decarboxylative arylation of quinoxalin-2(1H)-ones under additive-, metal catalyst-, and external photosensitizer-free and ambient conditions DOI
Long‐Yong Xie, Sha Peng, Lihua Yang

et al.

Green Chemistry, Journal Year: 2020, Volume and Issue: 23(1), P. 374 - 378

Published: Oct. 23, 2020

Aryl radicals were generated for the first time from aryl acyl peroxides in ethyl acetate under ambient conditions and visible-light illumination absence of any additive, metal catalyst, or external photosensitizer.

Language: Английский

Citations

121

Sustainable electrochemical cross-dehydrogenative coupling of 4-quinolones and diorganyl diselenides DOI
Jinyang Chen, Hongyu Wu, Qingwen Gui

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2021, Volume and Issue: 42(9), P. 1445 - 1450

Published: May 6, 2021

Language: Английский

Citations

92

Alkyl Carbazates for Electrochemical Deoxygenative Functionalization of Heteroarenes DOI
Yongyuan Gao, Zheng‐Guang Wu, Lei Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(27), P. 10859 - 10863

Published: March 30, 2020

The C-O bond cleavage for activation of alcohols is synthetically useful and practically challenging. This work describes carbazate as a new type electrochemically activated alkylating agent derived from ubiquitous direct functionalization heteroarenes under mild electrolytic conditions. simple undivided cell at low oxidative potentials with carbon/platinum electrode set-ups offers excellent substrate tolerance, affording variety primary, secondary tertiary alkyl-decorated heterocycles in good chemical yields. Furthermore, the mechanism this electrochemical deoxyalkylation reaction has been investigated.

Language: Английский

Citations

87