Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, 510641, Guangzhou, China.
School of Materials Science and Engineering, PFCM Lab, Sun Yat-sen University, 510275, Guangzhou, China.
Nat Commun. 2023 Apr 3;14(1):1862. doi: 10.1038/s41467-023-37299-x.
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.
[sigma]-重排反应为通过 C-C σ 键活化实现碳骨架的高原子经济性和步骤经济性的位点选择性重组提供了一种通用策略。在此，我们公开了一种通过 Mn(I)催化的 β,γ-不饱和醇的 [sigma]-重排反应，该反应通过 C-C σ 键活化实现。各种 α-芳基烯丙醇和 α-芳基炔丙醇可以通过原位 1,2-或 1,3-[sigma]-重排反应，在简单的催化体系下转化为复杂结构的芳基乙基和芳基乙烯基羰基化合物。更重要的是，这种催化模型可以通过双分子 [2n + 4] 偶联-环化和单分子 [n + 1] 环扩展进一步用于组装大环酮。所提出的骨架重排反应将是对传统分子重排的有益补充。
