Photoinduced regioselective difluorination of secondary inert C(sp<sup>3</sup>)–H bonds in sulfonamides <i>via</i> 1,5-hydrogen-atom transfer

Li, Jianjun; Chen, Zhi; Zhu, Wei; Wang, Chaodong; Xu, Nuo; Jin, Qichao; Huang, X. T.; Song, Shengjie

doi:10.1039/d3qo00931a

Cited by 3 publications

(1 citation statement)

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“…Our group recently reported a photo-catalyzed, selective remote secondary C(sp 3 )–H fluorination of a wide range of aliphatic sulfonamides. 17 Use of hypervalent iodine agents also provided a strategy to generate HCRs. 18 Considering that alcohols and amides are widely distributed in nature and are readily accessible, 19,20 we wondered whether site-selective cascade addition/cyclization on the carbon chains of free alcohols and amides via HCR-directed distal C(sp 3 )–H activation could achieve the desired molecular complexity.…”

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confidence: 99%

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp³)–H bonds

Huang,

Sun,

Sun

et al. 2024

Chem. Commun.

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confidence: 99%

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp³)–H bonds

Huang,

Sun,

Sun

et al. 2024

Chem. Commun.

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Photo- and electro-induced perfluoroalkylation/cyclization of o-hydroxyaryl enaminones: Synthesis of perfluoroalkyl chromones

Song,

Wang,

Sun

et al. 2024

Green Synthesis and Catalysis

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Site-Selective Functionalization of Unactivated C(sp3)–H Bonds via Synergistic Merger of Photoredox and HAT Catalysis

Li,

Wang,

Chen

et al. 2024

Preprint

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Hydrogen atom abstraction from C(sp3)−H substrates for the generation of alkyl radical represents a desirable yet underexplored strategy in alkylation reaction since involving noble metal catalysts, stoichiometric oxidants, and limited scope are common drawbacks. Here we describe the synergistic utilization of photoredox and hydrogen atom transfer (HAT) catalysis to accomplish a general and practical functionalization of unactived C(sp3)−H centers, which features broad reaction scope, high functional group compatibility, and operational simplicity. A combination of validation experiments and density functional theory reveals that the N-centred radicals, generated from free N−H bond via photoredox catalyzed single-electron oxidation followed by deprotonation in a stepwise electron/proton transfer event, are the key intermediates that enable an intramolecular 1,5-HAT or intermolecular HAT process for nucleophilic carbon-centred radicals formation to achieve heteroarylation, alkylation, amination, cyanation, azidation, trifluoromethylthiolation, halogenation and deuteration. The practical value of this protocol was further demonstrated by the gram-scale synthesis and the late-stage functionalization of natural products and drug derivatives.

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Photoinduced regioselective difluorination of secondary inert C(sp³)–H bonds in sulfonamides via 1,5-hydrogen-atom transfer

Abstract: Difluorinated compounds are important structural motifs in organic synthesis and medicinal chemistry because fluoride can modulate the properties of various molecules. In this paper, we present an efficient and convenient...

Cited by 3 publications

References 87 publications

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp³)–H bonds

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp³)–H bonds

Photo- and electro-induced perfluoroalkylation/cyclization of o-hydroxyaryl enaminones: Synthesis of perfluoroalkyl chromones

Site-Selective Functionalization of Unactivated C(sp3)–H Bonds via Synergistic Merger of Photoredox and HAT Catalysis

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Photoinduced regioselective difluorination of secondary inert C(sp3)–H bonds in sulfonamides via 1,5-hydrogen-atom transfer

Abstract: Difluorinated compounds are important structural motifs in organic synthesis and medicinal chemistry because fluoride can modulate the properties of various molecules. In this paper, we present an efficient and convenient...

Cited by 3 publications

References 87 publications

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp3)–H bonds

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp3)–H bonds

Photo- and electro-induced perfluoroalkylation/cyclization of o-hydroxyaryl enaminones: Synthesis of perfluoroalkyl chromones

Site-Selective Functionalization of Unactivated C(sp3)–H Bonds via Synergistic Merger of Photoredox and HAT Catalysis

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Photoinduced regioselective difluorination of secondary inert C(sp³)–H bonds in sulfonamides via 1,5-hydrogen-atom transfer

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp³)–H bonds

Regioselective synthesis of isoquinolinonediones through remote unactivated C(sp³)–H bonds