ja7b02725_si_002.cif (1.66 MB)
Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer
dataset
posted on 2017-04-18, 00:00 authored by Xiaoming Wang, Tobias Gensch, Andreas Lerchen, Constantin G. Daniliuc, Frank GloriusA 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.