Reaction Mechanism of an Intramolecular Oxime Transfer Reaction: A Computational Study

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• 作者：Jani Moilanen ; Antti Neuvonen ; Petri Pihko
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：March 7, 2014
• 年：2014
• 卷：79
• 期：5
• 页码：2006-2014
• 全文大小：510K
• 年卷期：v.79,no.5(March 7, 2014)
• ISSN：1520-6904

文摘

Density functional theory (PBE0/def2-TZVPP) calculations in conjunction with a polarizable continuum model were used to assess the mechanism of the intramolecular oxime transfer reaction that leads to the formation of isoxazolines. Different diastereomers of the intermediates as well as different oximes (formaldehyde and acetone oxime) were considered. The computed reaction profile predicts the water-addition and -expulsion steps as the highest barriers along the pathway, a conclusion that is in line with the experimental evidence obtained previously for these reactions.