Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (1): 190-195.DOI: 10.6023/cjoc201607005 Previous Articles     Next Articles



卞荣剑, 鲍晓光   

  1. 苏州大学材料与化学化工学部 苏州 215123
  • 收稿日期:2016-07-04 修回日期:2016-08-28 发布日期:2016-09-01
  • 通讯作者: 鲍晓光
  • 基金资助:

    国家自然科学基金(No. 21302133)资助项目.

Computational Insights into the Mechanism of Pd(0) and Ben-zoic Acid Co-Catalyzed Hydroamination of Internal Alkynes

Bian Rongjian, Bao Xiaoguang   

  1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123
  • Received:2016-07-04 Revised:2016-08-28 Published:2016-09-01
  • Supported by:

    Project supported by the National Natural Science Foundation of China(No. 21302133).

Computational studies were carried out to investigate the detailed mechanism of Pd(0) and benzoic acid co-catalyzed hydroamination of internal alkynes.In the presence of the benzoic acid,the formation of a hydridopalladium intermediate via the oxidative addition(OA) of the O-H bond of benzoic acid into the Pd(0) complex center might not be a favorable reaction pathway to start the reaction.Instead,after the coordination of benzoic acid with the Pd(0)-alkyne complex,a proton transfer process from the acid to carbon of alkyne is found to be a favorable pathway,leading to the alkenyl(PhCOO) Pd(Ⅱ) intermediate.Next,the resulting alkenyl(PhCOO) Pd(Ⅱ) species would produce phenylallene intermediate via a β-H elimination step assisted by the formed benzoate anion.Subsequently,the benzoic acid might undergo a second proton step to the phenylallene intermediate to produce the π-allylpalladium species.Finally,the amine substrate could undergo a nucleophilic addition to the terminal carbon of the π-allylpalladium species to produce the hydroamination product.

Key words: Pd catalysis, carboxylic acid, DFT, hydroamination, reaction mechanism