Theoretical study on the reaction mechanisms and stereoselectivities of DABCO‐catalyzed Rauhut–Currier/cyclization reaction of methyl acrylate with 2‐benzoyl‐3‐phenyl‐acrylonitrile |
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Authors: | Yan Li Shiwen Du |
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Affiliation: | School of Petroleum and Chemical Engineering, Dalian University of Technology, Panjin City, Liaoning Province, China |
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Abstract: | 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 R1 with (E)‐2‐benzoyl‐3‐phenyl‐acrylonitrile R2 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 R1 to form intermediates Int1 and Int1‐1, the second step is the reaction of Int1 and Int1‐1 with R2 to generate intermediate Int2(SS,RR,SR&RS), and the last step is an intramolecular SN2 process to give the final product P(SS,RR,SR&RS) and release catalyst DABCO. The SN2 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. |
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Keywords: | density functional theory Rauhut– Currier reaction reaction mechanisms stereoselectivity |
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