Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1925 - 2016

Published: Sept. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Language: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Recent advances in visible light-activated radical coupling reactions triggered by (i) ruthenium, (ii) iridium and (iii) organic photoredox agents

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(17), P. 9540 - 9685

Published: Jan. 1, 2021

Visible light-activated reactions continue to expand and diversify. The example shown here is a Birch reduction achieved by organophotoredox reagents.

Language: Английский

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Visible light photoredox-catalysed remote C–H functionalisation enabled by 1,5-hydrogen atom transfer (1,5-HAT)

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7359 - 7377

Published: Jan. 1, 2021

The generation of heteroatom-centred radicals followed by intramolecular 1,5-HAT and functionalisation the translocated carbon-centred radical is an efficient way to functionalize chemo- regio-selectively remote unactivated C(sp³)–H bond.

Language: Английский

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N‐Centered Radical Directed Remote C−H Bond Functionalization via Hydrogen Atom Transfer

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(6), P. 651 - 672

Published: Feb. 3, 2020

The N-centered radical directed remote C-H bond functionalization via hydrogen-atom-transfer at distant sites has developed as an enormous potential tool for the organic synthetic chemists. Unactivated and secondary tertiary, well selected primary bonds, can be utilized by following these methodologies. synthesis of heterocyclic scaffolds provides them extra attention modern days' developments in this field unactivated bonds functionalizations.

Language: Английский

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Remote C–C bond formationviavisible light photoredox-catalyzed intramolecular hydrogen atom transfer

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(24), P. 4519 - 4532

Published: Jan. 1, 2020

Visible light photoredox catalysis combined with intramolecular hydrogen atom transfer (HAT) can serve as a unique tool for achieving remote C–C bond formation. Recent advances in photoredox-catalyzed formation are summarized.

Language: Английский

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Copper-Catalyzed, Chloroamide-Directed Benzylic C–H Difluoromethylation

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(50), P. 19941 - 19949

Published: Nov. 22, 2019

We report herein the first catalytic strategy to harness amidyl radicals derived from N-chloroamides for C–C bond formation, allowing discovery of benzylic C–H difluoromethylation. Under copper-catalyzed conditions, a wide variety N-chlorocarboxamides and N-chlorocarbamates direct selective difluoromethylation with nucleophilic difluoromethyl source at room temperature. This scalable protocol exhibits broad substrate scope functional group tolerance, enabling late-stage bioactive molecules. copper-catalyzed, chloroamide-directed has also been extended pentafluoroethylation trifluoromethylation. Mechanistic studies on reactions support that involve formation via intramolecular activation, followed by copper-mediated transfer groups radicals.

Language: Английский

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Radical Functionalization of Remote C(sp ³ )–H Bonds Mediated by Unprotected Alcohols and Amides

CCS Chemistry, Journal Year: 2020, Volume and Issue: 2(5), P. 813 - 828

Published: June 10, 2020

Aliphatic alcohols and amides are highly valued, ubiquitous chemicals in synthetic chemistry. Radical-promoted regioselective functionalization of unactivated C(sp3)–H bonds offers an atom step...

Language: Английский

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Enantioselective Remote C(sp³)–H Cyanation via Dual Photoredox and Copper Catalysis

Organic Letters, Journal Year: 2020, Volume and Issue: 22(15), P. 5910 - 5914

Published: July 22, 2020

The remote C(sp3)-H cyanation of carboxamides has been described by merging photoredox and copper catalysis in a site-selective enantiocontrolled manner. protocol is the integration photoinduced nitrogen-centered radical-mediated intermolecular hydrogen atom transfer with chiral copper-complex-catalyzed radical cyanation. This strategy gives enantio-enriched cyanated amides high yields.

Language: Английский

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Remote C(sp³)−H Acylation of Amides and Cascade Cyclization via N‐Heterocyclic Carbene Organocatalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(15)

Published: Feb. 3, 2022

Abstract The direct functionalization of inert C(sp 3 )−H bonds under environmentally benign catalytic conditions remains a challenging task in synthetic chemistry. Here, we report an organocatalytic remote acylation amides and cascade cyclization through radical‐mediated 1,5‐hydrogen atom transfer mechanism using N‐heterocyclic carbene as the catalyst. Notably, diversity nitrogen‐containing substrates, including simple linear aliphatic carbamates ortho ‐alkyl benzamides, can be successfully applied to this system. With established protocol, over 120 examples functionalized δ‐amino ketones isoquinolinones with diverse substituents were easily synthesized up 99 % yield mild conditions. robustness generality strategy further highlighted by successful unactivated late‐stage modification pharmaceutical molecules. Then, asymmetric control radical reaction was attempted proven feasible newly designed chiral thiazolium catalyst, moderate enantioselectivity obtained at current stage. Preliminary mechanistic investigations several reactions, KIE experiments, computational studies shed light on mechanism.

Language: Английский

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