The allylic azide rearrangement: Achieving selectivity
The allylic azide rearrangement: Achieving selectivity
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DOI：
10.1021/ja050622q
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发表时间：
2005-10-05
影响因子：
15
通讯作者：
Fokin, VV
中科院分区：
文献类型：
--
作者：
Feldman, AK;Colasson, B;Fokin, VV
烯丙基叠氮化合物经历了快速的[3.3]-Sigmatroic重排，导致了几个异构体的动态平衡。因此，烯丙基叠氮化合物的反应通常会产生混合物。然而，即使是异构化的烯丙基叠氮化物的反应活性的微小差异也可以被放大，从而以良好的到优异的产率产生单一的产物。例如，铜(I)催化的与炔烃的环加成反应选择性地捕获了伯烯丙基叠氮异构体和仲烯丙基叠氮异构体，而MCPBA环氧化反应则有利于含有更多富含电子的双烯烃的异构体。
Allylic azides undergo a rapid [3.3]-sigmatropic rearrangement which results in dynamic equilibrium of several isomers. Thus, reactions of allylic azides usually result in mixtures of products. However, even small differences in reactivity of the isomeric allylic azides can be amplified to result in a single product in good to excellent yields. For example, the Cu(I)-catalyzed cycloaddition with alkynes selectively captures primary and secondary allylic azide isomers, whereas MCPBA epoxidation favors isomers which contain more electron-rich double olefins.