Issue 26, 2022

Catalytic defluorinative ketyl–olefin coupling by halogen-atom transfer


Ketyl–olefin coupling reactions stand as one of the fundamental chemical transformations in synthetic chemistry and have been widely employed in the generation of complex molecular architectures and natural product synthesis. However, catalytic ketyl–olefin coupling, until the recent development of photoredox chemistry and electrosynthesis through single-electron transfer mechanisms, has remained largely undeveloped. Herein, we describe a new approach to achieve catalytic ketyl–olefin coupling reactions by a halogen-atom transfer mechanism, which provides innovative and efficient access to various gem-difluorohomoallylic alcohols under mild conditions with broad substrate scope. Preliminary mechanistic experimental and computational studies demonstrate that this radical-to-polar crossover transformation could be achieved by sequentially orchestrated Lewis acid activation, halogen-atom transfer, radical addition, single-electron reduction and β-fluoro elimination.

Graphical abstract: Catalytic defluorinative ketyl–olefin coupling by halogen-atom transfer

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Article information

Article type
Edge Article
16 May 2022
09 Jun 2022
First published
10 Jun 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 7855-7862

Catalytic defluorinative ketyl–olefin coupling by halogen-atom transfer

P. Bellotti, H. Huang, T. Faber, R. Laskar and F. Glorius, Chem. Sci., 2022, 13, 7855 DOI: 10.1039/D2SC02732A

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