Mn(I)-catalyzed sigmatropic rearrangement of β, γ-unsaturated alcohols

作者：Yang, Can; Zhou, Xiaoyu; Shen, Lixing; Ke, Zhuofeng^*; Jiang, Huanfeng; Zeng, Wei^*

来源：Nature Communications, 2023, 14(1).

DOI：10.1038/s41467-023-37299-x

• CARBON-CARBON BOND
• CLAISEN REARRANGEMENT
• TRANSFORMATIONS
• CATALYSIS
• KETONES

Molecular rearrangements are ubiquitous in modern synthetic chemistry, providing a powerful strategy to arrive at complex structures in an atom- and step-economic process. Here, the authors disclose a Mn(I)- catalyzed sigmatropic rearrangement of beta, gamma-unsaturated alcohols via C-C sigma-bond activation to site-selectively reorganize carbon skeletons. @@@ 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 beta, gamma-unsaturated alcohols via C-C sigma bond activation. A variety of alpha-aryl-allylic alcohols and alpha-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.

• 单位
  中山大学