title: Theoretical study of the mechanism for the Markovnikov addition of imidazole to vinyl acetate catalyzed by the ionic liquid [bmIm]OH.
abstract: By performing density functional theory calculations, we have studied the Markovnikov addition of imidazole to vinyl acetate catalyzed by 1-butyl-3-methylimidazolium hydroxide, [bmIm]OH, a novel basic ionic liquid. The purpose is to show the detailed reaction mechanism, to rationalize the experimental observations, and in particular to better understand the role of [bmIm]OH played in the reaction as a catalyst. Two different reaction pathways (stepwise and concerted) have been characterized and analyzed in detail. It was found that both the cation and anion of [bmIm]OH play important roles in the Markovnikov addition, which decrease the barrier and increase the selectivity of Markovnikov addition. The present results rationalize the early experimental findings well and provide a prototype for theoretically understanding the Markovnikov addition catalyzed by room-temperature ionic liquids.
authors: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China.
authors: Hui
authors: H
authors: Sun
authors: Dongju
authors: D
authors: Zhang
authors: Fang
authors: F
authors: Wang
authors: Chengbu
authors: C
authors: Liu