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Issue 8, 2017
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Enantioselective catalytic β-amination through proton-coupled electron transfer followed by stereocontrolled radical–radical coupling

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Abstract

A new mechanistic approach for the catalytic, enantioselective conjugate addition of nitrogen-based nucleophiles to acceptor-substituted alkenes is reported, which is based on a visible light induced and phosphate base promoted transfer of a single electron from a nitrogen nucleophile to a catalyst-bound acceptor-substituted alkene, followed by a stereocontrolled C–N bond formation through stereocontrolled radical–radical coupling. Specifically, N-aryl carbamates are added to the β-position of α,β-unsaturated 2-acyl imidazoles using a visible light activated photoredox mediator in combination with a chiral-at-rhodium Lewis acid catalyst and a weak phosphate base, affording new C–N bonds in a highly enantioselective fashion with enantioselectivities reaching up to 99% ee and >99 : 1 dr for a menthol-derived carbamate. As an application, the straightforward synthesis of a chiral β-amino acid ester derivative is demonstrated.

Graphical abstract: Enantioselective catalytic β-amination through proton-coupled electron transfer followed by stereocontrolled radical–radical coupling

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Publication details

The article was received on 05 May 2017, accepted on 15 Jun 2017 and first published on 15 Jun 2017


Article type: Edge Article
DOI: 10.1039/C7SC02031G
Citation: Chem. Sci., 2017,8, 5757-5763
  • Open access: Creative Commons BY license
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    Enantioselective catalytic β-amination through proton-coupled electron transfer followed by stereocontrolled radical–radical coupling

    Z. Zhou, Y. Li, B. Han, L. Gong and E. Meggers, Chem. Sci., 2017, 8, 5757
    DOI: 10.1039/C7SC02031G

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