物理化学学报2011，Vol.27Issue(3)：577-583,7.
AuCl3催化2-(1-炔基)-2-烯基酮合成多取代呋喃的机理
Mechanism of AuCl3-Catalyzed Synthesis of Highly Substituted Furans Based on 2-(1-Alkynyl)-2-alken-1-ones
摘要
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.关键词
AuCl3/机理/密度泛函理论/呋喃/配体分类
化学化工引用本文复制引用
安小应,何荣幸,黄成,李明..AuCl3催化2-(1-炔基)-2-烯基酮合成多取代呋喃的机理[J].物理化学学报,2011,27(3):577-583,7.基金项目
教育部科学技术重点项目(104263)资助 （104263）
