Theoretical Study on the Catalytic Cycle and Ligands Effect for the Pd(II)-Catalyzed Heck Reaction

DOI Web Site Open Access
  • Sanada Shohei
    Graduate School of Science and Engineering, Yamaguchi University
  • Kuroda Takaaki
    Graduate School of Science and Engineering, Yamaguchi University
  • Sumimoto Michinori
    Graduate School of Science and Engineering, Yamaguchi University
  • Hori Kenji
    Graduate School of Science and Engineering, Yamaguchi University

Bibliographic Information

Other Title
  • N-N二座配位パラジウム(II)を用いたHeck反応の触媒サイクルと配位子効果に関する理論的研究

Description

The palladium-catalyzed Mizoroki-Heck reaction is one of the most widely used and important reactions in organic synthesis and organometallic chemistry. Since the ligand of Pd complex used as a catalyst influences a reaction, the search for ligands is one of the important work. In this study, we theoretically investigated the reaction mechanism of Mizoroki-Heck reaction with PdCl2(2-(2'-pyridyl) benzo azole) catalyst using the DFT method. From the calculated results, the active species was found to be Pd(Ph)(Br)(L) complex which produced by the reactive substrates. There are consisted of seven processes in this reaction mechanism, as follow: (1) ethylene coordination, (2) ethylene Insertion, (3) β-H Abstraction, (4) styrene elimination, (5) Ph-Br coordination, (6) H-Br elimination, and (7) Ph-Br oxidative addition. The rate-determining step is Ph-Br oxidative addition, and the values of the activation free energies were calculated to be 30-32 kcal/mol. From these results, it was suggested that this catalytic cycle is proceeded by Pd0/PdII, not PdII/PdIV.

Journal

  • Journal of Computer Aided Chemistry

    Journal of Computer Aided Chemistry 16 (0), 30-38, 2015

    Division of Chemical Information and Computer Sciences The Chemical Society of Japan

Keywords

Details 詳細情報について

Report a problem

Back to top