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Theoretical study on the reaction mechanisms and stereoselectivities of DABCO‐catalyzed Rauhut–Currier/cyclization reaction of methyl acrylate with 2‐benzoyl‐3‐phenyl‐acrylonitrile
Author(s) -
Li Yan,
Du Shiwen
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25325
Subject(s) - dabco , acrylonitrile , chemistry , methyl acrylate , catalysis , reaction mechanism , intramolecular force , stereoselectivity , medicinal chemistry , stereochemistry , organic chemistry , polymer , copolymer
With the aid of density functional theory (DFT) calculations, we have investigated the mechanisms and stereoselectivities of the tandem cross Rauhut–Currier/cyclization reaction of methyl acrylate R 1 with ( E )‐2‐benzoyl‐3‐phenyl‐acrylonitrile R 2 catalyzed by a tertiary amine DABCO. The results of the DFT calculations indicate that the favorable mechanism (mechanism A) includes three steps: the first step is the nucleophilic attack of DABCO on R 1 to form intermediates Int1 and Int1‐1, the second step is the reaction of Int1 and Int1‐1 with R 2 to generate intermediate Int2(SS,RR,SR&RS), and the last step is an intramolecular S N 2 process to give the final product P(SS,RR,SR&RS) and release catalyst DABCO. The S N 2 substitution is computed to be the rate‐determining step, whereas the second step is the stereoselectivity‐determining step. The present study may be helpful for understanding the reaction mechanism of similar tandem reactions.