Reactive Intermediates from DMDO Oxidation of Ynamides. Trapping of a de novo Chiral Push−Pull Carbene via Cyclopropanation

The reaction profile of DMDO oxidations of ynamides is described. This work illustrates the first examples of highly diastereoselective
intramolecular cyclopropanations of a push−pull carbene derived from alkyne oxidation. In addition, the ynamide oxidation provides facile
access to ketoimides and reveals mechanistic insights into the chemistry of electronically biased oxirenes.

本工作详细阐述了DMDO氧化亚胺的反应谱。该研究展示了由烯烃氧化衍生而来的推-拉型碳烯所进行的极具立体选择性的分子内环丙烷化反应的首次实例。此外，亚胺氧化反应能够简便地制备酮亚胺，并揭示了电子偏极化的环氧烯化学机理的见解。