Methylalkylation of Unactivated Alkenes by Photoredox/Nickel Catalytic HAT and Radical Selectivity Control

Herein, we report a strategy for the methylalkylation of unactivated alkenes via synergistic photoredox/nickel catalysis. This mild transformation employs di-<i>tert</i>-butyl peroxide (DTBP) as a bifunctional reagent, which serves simultaneously as a hydrogen atom transfer (HAT) reagent and a source of methyl radical, thereby facilitating the coupling of malonate-derived radicals with alkenes. By integrating HAT with radical selectivity control, the method enables the formation of two C(sp<sup>3</sup>)-C(sp<sup>3</sup>) bonds in a single synthetic operation, offering a streamlined route to valuable three-dimensional scaffolds.

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Publication Details

Journal
Organic Letters
Published
2026-02-05
DOI
https://doi.org/10.1021/acs.orglett.5c05168
Primary Topic
Radical Photochemical Reactions
Type
article
Field-Weighted Citation Impact
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article

Methylalkylation of Unactivated Alkenes by Photoredox/Nickel Catalytic HAT and Radical Selectivity Control

Yi Wang, Hao-Wen Jiang, Hui Zhang, Peng-Fei Xu
Organic Letters
Radical Photochemical Reactions
article

Methylalkylation of Unactivated Alkenes by Photoredox/Nickel Catalytic HAT and Radical Selectivity Control

Yi Wang, Hao-Wen Jiang, Hui Zhang, Peng-Fei Xu
article en

Abstract

Herein, we report a strategy for the methylalkylation of unactivated alkenes via synergistic photoredox/nickel catalysis. This mild transformation employs di-<i>tert</i>-butyl peroxide (DTBP) as a bifunctional reagent, which serves simultaneously as a hydrogen atom transfer (HAT) reagent and a source of methyl radical, thereby facilitating the coupling of malonate-derived radicals with alkenes. By integrating HAT with radical selectivity control, the method enables the formation of two C(sp<sup>3</sup>)-C(sp<sup>3</sup>) bonds in a single synthetic operation, offering a streamlined route to valuable three-dimensional scaffolds.

Organic LettersVol. 28(7)
Frontier Science Foundation (CH), State Key Laboratory of Chemical Engineering (CN), Lanzhou University (CN)
Openalex Percentile: Top 64%
Radical Photochemical Reactions
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