A theoretical study on the mechanisms of intermolecular hydroacylation of aldehyde catalyzed by neutral and cationic rhodium complexes  

作　　者：WANG Min ZHANG Xin CHEN Zhuo TANG YanHui LEI Ming 

机构地区：[1]State Key Laboratory of Chemical Resource Engineering,Institute of Materia Medica,College of Science,Beijing University of Chemical Technology [2]College of Materials Science and Engineering,Beijing Institute of Fashion Technology

出　　处：《Science China Chemistry》2014年第9期1264-1275,共12页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21373023,21203006,21072018)

摘　　要：In this paper, we used density functional theory(DFT) computations to study the mechanisms of the hydroacylation reaction of an aldehyde with an alkene catalyzed by Wilkinson's catalyst and an organic catalyst 2-amino-3-picoline in cationic and neutral systems. An aldehyde's hydroacylation includes three stages: the C–H activation to form rhodium hydride(stage I), the alkene insertion into the Rh–H bond to give the Rh-alkyl complex(stage II), and the C–C bond formation(stage III). Possible pathways for the hydroacylation originated from the trans and cis isomers of the catalytic cycle. In this paper, we discussed the neutral and cationic pathways. The rate-determining step is the C–H activation step in neutral system but the reductive elimination step in the cationic system. Meanwhile, the alkyl group migration-phosphine ligand coordination pathway is more favorable than the phosphine ligand coordination-alkyl group migration pathway in the C–C formation stage. Furthermore, the calculated results imply that an electron-withdrawing group may decrease the energy barrier of the C–H activation in the benzaldehyde hydroacylation.In this paper, we used density functional theory （DFT） computations to study the mechanisms of the hydroacylation reaction of an aldehyde with an alkene catalyzed by Wilkinson＇s catalyst and an organic catalyst 2-amino-3-picoline in cationic and neu- tral systems. An aldehyde＇s hydroacylation includes three stages： the C-H activation to form rhodium hydride （stage I）, the al- kene insertion into the Rh-H bond to give the Rh-alkyl complex （stage II）, and the C-C bond formation （stage III）. Possible pathways for the hydroacylation originated from the trans and cis isomers of the catalytic cycle. In this paper, we discussed the neutral and cationic pathways. The rate-determining step is the C-H activation step in neutral system but the reductive elimination step in the cationic system. Meanwhile, the alkyl group migration-phosphine ligand coordination pathway is more favorable than the phosphine ligand coordination-alkyl group migration pathway in the C-C formation stage. Furthermore, the calculated results imply that an electron-withdrawing group may decrease the energy barrier of the C-H activation in the benzaldehyde hydroacylation.

关 键 词：C-H activation DFT HYDROACYLATION metal organic cooperative catalyst reaction mechanism rhodium complex 

分 类 号：O641[理学—物理化学]