TY - DATA T1 - Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C–H Bond Amidation by Intramolecular Amide Transfer PY - 2017/04/18 AU - Xiaoming Wang AU - Tobias Gensch AU - Andreas Lerchen AU - Constantin G. Daniliuc AU - Frank Glorius UR - https://acs.figshare.com/articles/journal_contribution/Cp_Rh_III_Bicyclic_Olefin_Cocatalyzed_C_H_Bond_Amidation_by_Intramolecular_Amide_Transfer/4907408 DO - 10.1021/jacs.7b02725.s001 L4 - https://ndownloader.figshare.com/files/8255156 KW - Cocatalyzed KW - cleavable KW - Olefin KW - Intramolecular Amide Transfer KW - phenoxyacetamide derivatives KW - Rh KW - Amidation KW - proceeding KW - species KW - methodology KW - role KW - late-stage diversification KW - intramolecular amide transfer KW - amidation KW - nitrenoid KW - moiety KW - ortho position KW - bicyclic olefin KW - Bond KW - cocatalyst KW - oxidative addition KW - Cp KW - bond N2 - 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. ER -