Leveraging triatropic rearrangements for stereoselective skeletal reshuffling

• 成果类型: Article
• 署名作者: Niu, Yuan; Chen, Yu; Zhou, Meng; Zeng, Huihui; Wang, Ke; Yu, Peiyuan; Dong, Zhe
• 署名单位: Southern University of Science & Technology; Southern University of Science & Technology
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-8075; 1095-9203
• DOI: 10.1126/science.adw3340
• 发表日期: 2026-01-08
• 页码: 171-178
• 关键词: DYOTROPIC REARRANGEMENTS; 2; 2-DISUBSTITUTED EPOXIDES; RESOLUTION; route; cycloadditions; TRANSFORMATION; complexes; oxidation; arylation; aldehydes

摘要

Pericyclic reactions transform simple precursors into architecturally complex products with exquisite stereocontrol, making them central tools in synthesis. Here, we report a class of pericyclic reactions, called triatropic rearrangements, wherein three sigma-bonds are broken concomitantly with the formation of two sigma-bonds and one pi-bond, all in a single transition state. Within this mechanistic manifold, carbon-oxygen bonds in epoxides are stereoselectively converted into carbon-carbon bonds in a process mediated by organoboron reagents. Epoxycycloalkanes undergo highly chemo-, regio-, and stereoselective carbon migration to furnish ring-contracted products with broad generality. This strategy also enables enantioselective 1,2-hydride migrations for linear epoxide substrates. The combination of this ring contraction protocol with [4+2] cycloadditions provides a distinct [4+2-1] strategy for the stereoselective construction of complex cyclopentanes in a modular fashion.