温斯坦重排反应：机理，控制和转化
Winstein Rearrangement: Mechanism, Control, and Transformation
DOI: 10.12677/jocr.2025.134041, PDF,   
作者: 郑丁铭*, 张 轩：浙江师范大学，化学与材料科学学院，浙江 金华
关键词: 温斯坦重排；叠氮；烯丙基叠氮化合物；Winstein Rearrangement； Azide； Allylic Azides
摘要: 有机叠氮化合物作为一类极为重要的合成中间体，具有广泛的反应活性。与多数有机叠氮化合物不同，烯丙基叠氮化合物具有独特的性质，能够自发地经历重排过程，生成多种异构体的混合物，这种重排反应被称为温斯坦重排。由于温斯坦重排的存在，在某些条件下使用烯丙基叠氮化合物会导致反应产率低和叠氮化合物的外消旋化。科学家们致力于揭示温斯坦重排的机理，并探索如何有效利用这一过程。可以使用几个指导原则来判断哪些叠氮化合物会产生异构体混合物，哪些会抑制重排。可以通过选择性反应条件以动态方式区分叠氮化合物的异构体。本文综述了烯丙基叠氮化合物的合成方法、反应活性、温斯坦重排的机理以及如何选择性利用叠氮化合物异构体。
Abstract: Organic azides are useful synthetic intermediates, which demonstrate broad reactivity. Unlike most organic azides, allylic azides can spontaneously rearrange to form a mixture of isomers. This rearrangement has been named the Winstein rearrangement. Using allylic azides can result in low yields and azide racemization in some synthetic contexts due to the Winstein rearrangement. Effort has been made to understand the mechanism of the Winstein rearrangement and to take advantage of this process. Several guiding principles can be used to identify which azides will produce a mixture of isomers and which will resist rearrangement. Selective reaction conditions can be used to differentiate the azide isomers in a dynamic manner. This review covers all aspects of allylic azides including their synthesis, their reactivity, the mechanism of the Winstein rearrangement, and reactions that can selectively elaborate an azide isomer.
文章引用：郑丁铭, 张轩. 温斯坦重排反应：机理，控制和转化[J]. 有机化学研究, 2025, 13(4): 423-434. https://doi.org/10.12677/jocr.2025.134041

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