title: Mechanistic insight on (E)-methyl 3-(2-aminophenyl)acrylate cyclization reaction by multicatalysis of solvent and substrate.
abstract: The reaction mechanism of (E)-methyl 3-(2-aminophenyl)acrylate (A) with phenylisothiocyanate (B) as well as the vital roles of substrate A and solvent water were investigated under unassisted, water-assisted, substrate A-assisted, and water-A-assisted conditions. The reaction proceeds with four processes via nucleophilic addition, deprotonation and protonation, intramolecular cyclization with hydrogen transfer, and keto-enol tautomerization. According to the different H-shift mode, two possible types of H-shift P1 and P2 are carefully investigated to identify the most preferred pathway, differing in the NH2 group deprotonation and CH group of A protonation processes. It is found that substrate A and water not only act as reactant and solvent, but also as catalyst, proton shuttle, and stabilizer in effectively lowering the energy barrier. Therefore, the results demonstrate that the strong donating and accepting ability of NH2 group on A and the presence of bulk water are the keys to the title reaction proceed. © 2016 Wiley Periodicals, Inc.
authors.affiliation: Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Renmin Street 5268#, Changchun, 130024, China.
authors.forename: Jiahui
authors.initials: J
authors.lastname: Liu
authors.affiliation: Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Renmin Street 5268#, Changchun, 130024, China.
authors.forename: Yiying
authors.initials: Y
authors.lastname: Zheng
authors.affiliation: Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Renmin Street 5268#, Changchun, 130024, China.
authors.forename: Ying
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Renmin Street 5268#, Changchun, 130024, China. jpzhang@nenu.edu.cn.
authors.forename: Haiyan
authors.initials: H
authors.lastname: Yuan
authors.affiliation: Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Renmin Street 5268#, Changchun, 130024, China. yuanhy034@nenu.edu.cn.
authors.forename: Jingping
authors.initials: J
authors.lastname: Zhang
keywords: (E)-methyl 3-(2-aminophenyl)acrylate; DFT; mechanism; multi-catalysis; water