Hydroalkynylation of Enamides Using Iridium or Rhodium Complexes: DFT Study on the Mechanism and Regioselectivity

DFT calculations have been carried out to study the mechanisms and origin of regioselectivity in Rh- and Ir-catalyzed hydroalkynylation of enamides with terminal alkynes. The two reactions, despite being catalyzed by the same group of transition metals, follow different reaction mechanisms. Through detailed DFT calculations, insight into the mechanisms is obtained and the different regioselectivity is understood.