Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (03): 577-583.doi: 10.3866/PKU.WHXB20110338

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Mechanism of AuCl3-Catalyzed Synthesis of Highly Substituted Furans Based on 2-(1-Alkynyl)-2-alken-1-ones

AN Xiao-Ying, HE Rong-Xing, HUANG Cheng, LI Ming   

  1. College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. China
  • Received:2010-10-17 Revised:2010-12-28 Published:2011-03-03
  • Contact: LI Ming E-mail:liming@swu.edu.cn
  • Supported by:

    The project was supported by the Science and Technology Foundation of Ministry of Education, China (104263).

Abstract:

We investigated the mechanism of the AuCl3-catalyzed synthesis of highly substituted furans from 2-(1-alkynyl)-2-alken-1-ones with nucleophiles using the density functional theory (DFT) with B3LYP function, and obtained the optimal pathway. The rate-determining step of the cyclization is H-migration from the hydroxy group to a ligand Cl of AuCl3 with a 49.3 kJ·mol-1 energy barrier. The calculated results show that the ligand Cl of AuCl3 plays an important role in the reaction, which stabilizes the catalyst and is also directly involved in the reaction. The active energy of proton transfer decreases from 71.5 to 49.3 kJ·mol-1 by assisting the proton transfer. In addition, the reason why HBF4 cannot catalyze the cyclization of 2-(1-alkynyl)-2-alken-1-ones is also discussed in this work. The theoretical results are consistent with the experimental observations.

Key words: AuCl3, Mechanism, Density functional theory, Furan, Ligand

MSC2000: 

  • O641