A novel “umpolung” intramolecular cyclization of alkynyl imines, in which the electrophilic imine sp²‐carbon formally serves as a nucleophilic site, was developed under Brønsted base catalysis. The reaction involves the unprecedented catalytic generation of α‐aminoester enolates from α‐iminoesters via the 1,2‐addition of the anion of a secondary phosphite to an imine moiety followed by the [1,2]‐rearrangement of a dialkoxyphosphoryl moiety from carbon to nitrogen, which is a formal umpolung process, and the intramolecular addition to an alkyne. This is a rare example of a [1,2]‐rearrangement of a dialkoxyphosphoryl moiety from carbon to nitrogen to generate an α‐amino carbanion and the first catalytic carbon–carbon bond forming reaction utilizing the resulting carbanion as a nucleophile.

中文翻译：

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Brønsted碱催化炔亚胺的分子内环化

在Brønsted碱催化下，开发了炔基亚胺的新型“分子环”分子内环化反应，其中亲电子亚胺sp ²碳正式用作亲核位点。该反应涉及通过亚磷酸亚乙酯的阴离子1,2-亚胺部分的亚胺加成反应，然后由碳中的二烷氧基磷酰基基团[1,2]重排，从而由α-亚氨基酯前所未有地催化生成α-氨基酯烯酸酯。氮，这是一个正式的化学过程，分子内添加到炔烃中。这是一个罕见的例子，是将二烷氧基磷酰基部分从碳到氮的[1,2]重排以生成α-氨基碳负离子，以及第一个催化碳-碳键形成反应，利用所得的碳负离子作为亲核试剂。