Sigmatropic rearrangement provides a versatile strategy to site-selectively reorganize carbon-skeleton with high atom- and step-economy. Herein, we disclose a Mn(I)-catalyzed sigmatropic rearrangement of β, γ-unsaturated alcohols via C-C σ bond activation. A variety of α-aryl-allylic alcohols and α-aryl-propargyl alcohols could undergo in-situ 1,2- or 1,3- sigmatropic rearrangements to allow for converting to complex structural arylethyl- and arylvinyl- carbonyl compounds under a simple catalytic system. More importantly, this catalysis model can be further applied to assemble macrocyclic ketones through bimolecular [2n + 4] coupling-cyclization and monomolecular [n + 1] ring-extension. The presented skeleton rearrangement would be a useful tool complementary to the traditional molecular rearrangement.

Sigmatropic 重排提供了一种多功能策略，可以以高原子经济性和步进经济性对碳骨架进行位点选择性重组。在此，我们公开了一种通过 CC σ 键激活实现的 Mn(I) 催化的 β, γ-不饱和醇的 sigmatropic 重排。多种 α-芳基-烯丙醇和 α-芳基-炔丙醇可以进行原位 1,2- 或 1,3- σ 重排，以允许在简单的催化下转化为复杂结构的芳乙基和芳基乙烯基羰基化合物系统。更重要的是，该催化模型可以进一步应用于通过双分子[2n + 4]偶联环化和单分子[n + 1]环延伸组装大环酮。提出的骨架重排将是对传统分子重排的补充的有用工具。