Reactivity of Alkynyl Metal Carbenoids: DFT Study on the Pt-Catalyzed Cyclopropanation of Propargyl Ester Containing 1,3-Diynes

This is the authors' abstract. We don't add key points for this paper.

DFT/M06 calculations were performed to investigate the mechanism of the Pt-catalyzed intermolecular cyclopropanation of propargyl ester containing diynes with styrene. The results show that the alkynyl Pt-carbenoid formed from proximal activation of the diyne is a more favorable productive intermediate for cyclopropanation, which occurs preferentially at the distal sp-hybridized carbon via an S(N)2'-type olefin addition. Notably, the widely accepted [1,3]-metallotropic shift of such an alkynyl metal carbenoid is found to be energetically demanding.