title: Reactivity of alkynyl metal carbenoids: DFT study on the Pt-catalyzed cyclopropanation of propargyl ester containing 1,3-diynes.
abstract: 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.
authors: College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035, PR China.
authors: Genping
authors: G
authors: Huang
authors: Kelei
authors: K
authors: Xie
authors: Daesung
authors: D
authors: Lee
authors: Yuanzhi
authors: Y
authors: Xia