Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 25, Issue 70, Pages 16120-16127Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201904111
Keywords
benzophenone; C-H activation; copper; Giese reaction; photocatalysis
Categories
Funding
- CNRS, the University of Bordeaux
- Ministere de l'Enseignement Superieur de la Recherche et de l'Innovation
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Photocatalyzed Giese-type alkylations of C(sp(3))-H bonds are very attractive reactions in the context of atom-economy in C-C bond formation. The main limitation of such reactions is that when using highly polymerizable olefin acceptors, such as unsubstituted acrylates, acrylonitrile, or methyl vinyl ketone, radical polymerization often becomes the dominant or exclusive reaction pathway. Herein, we report that the polymerization of such olefins is strongly limited or suppressed when combining the photocatalytic activity of benzophenone (BP) with a catalytic amount of Cu(OAc)(2). Under mild and operationally simple conditions, the Giese adducts resulting from the C(sp(3))-H functionalization of amines, alcohols, ethers, and cycloalkanes could be synthesized. Preliminary mechanistic studies have revealed that the reaction does not proceed through a radical chain, but through a dual BP/Cu photocatalytic process, in which both Cu-II and low-valent Cu-I/0 species, generated in situ by reduction by the BP ketyl radical, may react with alpha-keto or alpha-cyano intermediate radicals, thus preventing polymerization.
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