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Mechanistic insight on ( E )‐methyl 3‐(2‐aminophenyl)acrylate cyclization reaction by multicatalysis of solvent and substrate
Author(s) -
Liu Jiahui,
Zheng Yiying,
Liu Ying,
Yuan Haiyan,
Zhang Jingping
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24463
Subject(s) - deprotonation , protonation , chemistry , tautomer , substrate (aquarium) , solvent , catalysis , intramolecular force , photochemistry , methyl acrylate , acrylate , enol , solvent effects , medicinal chemistry , reaction mechanism , organic chemistry , ion , oceanography , monomer , copolymer , geology , polymer
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 NH 2 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 NH 2 group on A and the presence of bulk water are the keys to the title reaction proceed. © 2016 Wiley Periodicals, Inc.