铜催化的酮亚胺与原位生成的亚铵离子反应：α,β-不饱和脒的合成。

Copper-catalyzed reaction of ketenimine and in situ generated immonium ion: access to α,β-unsaturated amidines.

出版信息

J Org Chem. 2014 Feb 7;79(3):936-42. doi: 10.1021/jo402368x.

Abstract

A Cu-catalyzed three-component reaction of alkyne, azides (sulfonyl or phosphoryl azides), and N,N-dialkyloxyformamide dialkyl acetal via electrophilic addition of immonium ion to copper ketenimine is reported. This new protocol for the preparation of α,β-unsaturated amidine derivatives appears to offer high yield, mild conditions, and wide substrate scope. The reaction might involve the processes of copper ketenimine intermediate formation, electrophilic addition, and isomerization.

摘要

本文报道了一种通过铜催化的炔烃、叠氮化物（磺酰基或膦酰基叠氮化物）和 N,N-二烷氧基甲酰胺二烷基缩醛的三组分反应，通过亚铵离子对铜烯酮亚胺的亲电加成来合成α,β-不饱和脒衍生物。这种新的制备α,β-不饱和脒衍生物的方法具有产率高、条件温和、底物范围广等优点。反应可能涉及铜烯酮亚胺中间体的形成、亲电加成和异构化过程。