Mechanistic insight on (E)-methyl 3-(2-aminophenyl)acrylate cyclization reaction by multicatalysis of solvent and substrate

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• 作者：Jiahui Liu ; Yiying Zheng ; Ying Liu ; Haiyan Yuan and Jingping Zhang
• 刊名：Journal of Computational Chemistry
• 出版年：2016
• 出版时间：October 5, 2016
• 年：2016
• 卷：37
• 期：26
• 页码：2386-2394
• 全文大小：931K
• ISSN：1096-987X

文摘

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.