Molecular dynamics of the intramolecular 1, 3-dipolar ene reaction of a nitrile oxide and an alkene: non-statistical behavior of a reaction involving a diradical intermediate* |
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Authors: | Yanmin Yu |
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Institution: | 1. Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, Beijing University of Technology, Beijing, People’s Republic of China;2. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA |
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Abstract: | ABSTRACTPotential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase. |
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Keywords: | Molecular reaction dynamics intramolecular 1 3-dipolar cycloaddition carbene-type mechanism diradical intermediate |
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