Directed carbonylative (3+1+2) cycloadditions of amino-substituted cyclopropanes and alkynes: reaction development and increased efficiencies using a cationic rhodium system

Urea-directed carbonylative insertion of Rh(I)-catalysts into one of the two proximal C-C bonds of aminocyclopropanes generates rhodacyclopentanone intermediates. These are trapped by N-tethered alkynes to provide a (3+1+2) cycloaddition protocol that accesses N-heterobicyclic enones. Stoichiometric studies on a series of model rhodacyclopentanone complexes outline key structural features and provide a rationale for the efficacy of urea directing groups. A comprehensive evaluation of cycloaddition scope and a 'second generation' cationic Rh(I)-system, which provides enhanced yields and reaction rates for challenging substrates, are presented. (C) 2015 The Authors. Published by Elsevier Ltd.