Journal of the American Chemical Society
Journal of the American Chemical Society
4 years ago

Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer

Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer
Frank Glorius, Xiaoming Wang, Tobias Gensch, Andreas Lerchen, Constantin G. Daniliuc
A bicyclic olefin was discovered as a cocatalyst in a Cp*Rh(III)-catalyzed C–H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O–N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C–H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02725

DOI: 10.1021/jacs.7b02725

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