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. 2016 Mar 14;55(12):4040-3.
doi: 10.1002/anie.201511438. Epub 2016 Feb 17.

Direct Acylation of C(sp(3))-H Bonds Enabled by Nickel and Photoredox Catalysis

Candice L Joe  1 , Abigail G Doyle  2
Affiliations

Direct Acylation of C(sp(3))-H Bonds Enabled by Nickel and Photoredox Catalysis

Candice L Joe et al. Angew Chem Int Ed Engl. .

Abstract

Using nickel and photoredox catalysis, the direct functionalization of C(sp(3))-H bonds of N-aryl amines by acyl electrophiles is described. The method affords a diverse range of α-amino ketones at room temperature and is amenable to late-stage coupling of complex and biologically relevant groups. C(sp(3))-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp(3))-C coupling. The merger of these two modes of catalysis leverages nickel's unique properties in alkyl cross-coupling while avoiding limitations commonly associated with transition-metal-mediated C(sp(3))-H activation, including requirements for chelating directing groups and high reaction temperatures.

Keywords: C−H activation; acylation; cross-coupling; nickel; photochemistry.

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Figures

Figure 1
Figure 1
Metallaphotoredox C(sp3)–H cross-coupling with acyl electrophiles. SM=starting material.
See this image and copyright information in PMC

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