近日，南方科技大学董哲团队实现了利用三中心重排进行立体选择性框架重组。相关论文于2026年1月8日发表在《科学》杂志上。

周环反应可将简单前体转化为具有精细立体控制的结构复杂产物，使其成为合成的核心工具。

研究组报道了一类被称为三中心重排的周环反应，即在单一过渡态中同步断裂三个σ键，同时形成两个σ键和一个π键。在这种机制框架下，环氧化物中的碳-氧键可通过有机硼试剂的介导，被立体选择性地转化为碳-碳键。环氧环烷烃经过高度的化学、区域和立体选择性碳迁移，使缩环产物具有广泛的普遍性。该策略还实现了线性环氧化物底物的对映选择性1,2-氢迁移。这种缩环方案与[4+2]环加成的结合，为以模块化方式立体选择性构建复杂环戊烷提供了一种独特的“[4+2-1]”策略。

附：英文原文

Title: Leveraging triatropic rearrangements for stereoselective skeletal reshuffling

Author: Yuan Niu, Yu Chen, Meng Zhou, Huihui Zeng, Ke Wang, Peiyuan Yu, Zhe Dong

Issue&Volume: 2026-01-08

Abstract: 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 σ-bonds are broken concomitantly with the formation of two σ-bonds and one π-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.

DOI: adw3340

Source: https://www.science.org/doi/10.1126/science.adw3340