Interruption of Formal Schmidt Rearrangement/Hosomi-Sakurai Reaction of Vinyl Azides with Allyl/Propargylsilanes

Guichun Fang, Zhenhua Liu, Shanshan Cao, Haiyan Yuan, Jingping Zhang*, Ling Pan*

*Jilin Province Key Laboratory of Organic Functional Molecular, Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, China, Email: zhangjp162nenu.edu.cn, panl948nenu.edu.cn

G. Fang, Z. Liu, S. Cao, H. Yuan, J. Zhang, L. Pan, Org. Lett., 2018, 20, 7113-7116.

DOI: 10.1021/acs.orglett.8b03062

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Abstract

BF₃·Et₂O promotes an interrupted Schmidt rearrangement/Hosomi-Sakurai reaction of N-tosyl vinyl azides via denitrogenative fragmentation, generation of a stabilized carbocation, which further undergoes nucleophilic addition by allyl/propargylsilanes for C-C bond formation. The reaction provides various homoallylic/allenylic amines in good yields under mild reaction conditions with well-defined functional-group tolerance.

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proposed reaction pathway

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Key Words

homoallylic amines, allenes, Schmidt Rearrangement, Hosomi-Sakurai Reaction

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ID: J54-Y2018