A Mechanistic Study on the Amidation of Esters Mediated by Sodium Formamide

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• 作者：Antonio Ramirez ; Boguslaw Mudryk ; Lucius Rossano ; Srinivas Tummala
• 刊名：The Journal of Organic Chemistry
• 出版年：2012
• 出版时间：January 6, 2012
• 年：2012
• 卷：77
• 期：1
• 页码：775-779
• 全文大小：317K
• 年卷期：v.77,no.1(January 6, 2012)
• ISSN：1520-6904

文摘

Kinetic and computational studies on the amidation of esters with mixtures of formamide and sodium methoxide are described. Rate studies are consistent with a fast deprotonation of formamide followed by two reversible acyl transfers affected by solvent participation. MP2 calculations suggest that the first acyl transfer between the ester and sodium formamide is rate-determining. The transition structures leading to the formation and collapse of the first tetrahedral intermediate are calculated to be isoenergetic.