Tandem Addition of Phosphite Nucleophiles Across Unsaturated Nitrogen-Containing Systems: Mechanistic Insights on Regioselectivity

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• 作者：Wouter Debrouwer ; Dietmar Hertsen ; Thomas S. A. Heugebaert ; Esma Birsen Boydas ; Veronique Van Speybroeck ; Saron Catak ; Christian V. Stevens
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：January 6, 2017
• 年：2017
• 卷：82
• 期：1
• 页码：188-201
• 全文大小：702K
• ISSN：1520-6904

文摘

The addition of phosphite nucleophiles across linear unsaturated imines is a powerful and atom-economical methodology for the synthesis of aminophosphonates. These products are of interest from both a biological and a synthetic point of view: they act as amino acid transition state analogs and Horner–Wadsworth–Emmons reagents, respectively. In this work the reaction between dialkyl trimethylsilyl phosphites and α,β,γ,δ-diunsaturated imines was evaluated as a continuation of our previous efforts in the field. As such, the first conjugate 1,6-addition of a phosphite nucleophile across a linear unsaturated N-containing system is reported herein. Theoretical calculations were performed to rationalize the observed regioselectivites and to shed light on the proposed mechanism.