烯丙基烯酮亚胺结构的[3,3]-重排反应研究进展

Recent Progress of [3,3]-Rearrangement Reaction of Allyl Ketenimine Structure

[3,3]-重排反应是合成化学中的重要反应类型,众多人名反应都经历了这一过程。然而,一类具有独特反应性的、含烯丙基烯酮亚胺结构的[3,3]-重排反应,却未得到应有的关注。本文将对这类重排反应进行分析和总结。该类反应的核心是构建具有烯丙基烯酮亚胺结构的重排前体。通过文献调研,我们发现这类重排前体,可以通过四种方式构建,包括1) 酰胺脱水,2) γ,δ-不饱和腈和烯酮亚胺的异构化,3) 烯丙基亚氨基磷酸酯与烯酮或酰氯反应,4) Pd催化介导等其他方式。随着烯酮亚胺结构的[3,3]-重排反应的发展,该类反应将成为制备腈类化合物和C-C键形成的重要方法。

[3,3]-rearrangement reaction is an important type of reaction in synthetic chemistry. Many name reactions involve this process. However, [3,3]-rearrangement of allyl ketenimine moieties exhibiting unique reactivities has not received much attention. This article summarizes this type of rearrangement reaction. The key step of these reactions is the construction of a rearrangement precursor having allyl ketenimine structures. Through literature analysis, we found that this type of rearrangement precursors can be constructed in four ways, including amide dehydration, heterogeneous between γ,δ-unsaturated nitriles and ketene imines, reactions of allyl iminophosphoranes with ketenes and acyl chlorides, Pd catalytic mediation and others. With the development of [3,3]-rearrangement reaction of ketenimine compounds, this type of reaction will become a powerful method for the synthesis of nitriles and construction of C-C bonds.