PhotoinducedCopper-Catalyzed Radical Mizoroki–HeckReaction with Unactivated Alkyl Iodide

Herein, we present a method for copper-catalyzed photoinduced radical Mizoroki–Heck (M-H) reactions utilizing unactivated alkyl iodides and styrene. This approach enables the smooth generation of (<i>E</i>)-olefin products with a good functional group tolerance, demonstrating broad applicability. The mechanism involves the in situ formation of a copper complex that binds to the alkyl iodide, leading to radical fragmentation under visible-light irradiation. This process generates alkyl radicals and a persistent copper(II) radical complex, both of which are crucial for subsequent olefin formation. Primary mechanistic studies support the photoinduced cleavage of the C(sp<sup>3</sup>)–I bond via an inner-sphere electron transfer (ISET) process involving an excited Cu(I) complex associated with the alkyl iodide. Finally, the formation of the M-H product occurs via a base-assisted β-H elimination process.

Publication Details

Journal
Figshare
Published
2025-03-28
DOI
https://doi.org/10.1021/acs.orglett.5c00602.s001
Primary Topic
Radical Photochemical Reactions
Type
article
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article

PhotoinducedCopper-Catalyzed Radical Mizoroki–HeckReaction with Unactivated Alkyl Iodide

Figshare
Radical Photochemical Reactions
article

PhotoinducedCopper-Catalyzed Radical Mizoroki–HeckReaction with Unactivated Alkyl Iodide

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Abstract

Herein, we present a method for copper-catalyzed photoinduced radical Mizoroki–Heck (M-H) reactions utilizing unactivated alkyl iodides and styrene. This approach enables the smooth generation of (<i>E</i>)-olefin products with a good functional group tolerance, demonstrating broad applicability. The mechanism involves the in situ formation of a copper complex that binds to the alkyl iodide, leading to radical fragmentation under visible-light irradiation. This process generates alkyl radicals and a persistent copper(II) radical complex, both of which are crucial for subsequent olefin formation. Primary mechanistic studies support the photoinduced cleavage of the C(sp<sup>3</sup>)–I bond via an inner-sphere electron transfer (ISET) process involving an excited Cu(I) complex associated with the alkyl iodide. Finally, the formation of the M-H product occurs via a base-assisted β-H elimination process.

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Radical Photochemical Reactions
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