Synthesis and structures of gold and copper carbene intermediates in catalytic amination of alkynes.

ABSTRACT: Metal carbenes are often proposed as reactive intermediates in the late transition metal-catalysed transformations of alkynes. Owing to their high reactivity, however, isolation and structural characterization of metal carbene intermediates in these transformations has remained unknown. Herein, we report the isolation of two acyclic gold and copper carbene intermediates in either Au(I)- or Cu(I)-catalysed cyclization of N-alkynyl formamidines through five-exo-dig cyclization. X-ray diffraction, ¹³C NMR spectra data and computational analyses provide evidence for the formation of a gold carbene intermediate with a carbocation-like electronic character. Using the intrinsic bond orbital (IBO) approach, we also evaluate the π-stabilizing effects of organic substituents at the carben

SUBMITTER: Wang J 

PROVIDER: S-EPMC5343500 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature