近日，浙江师范大学彭勃团队实现了通过重芳化阻断磺胺克莱森重排的不对称脱芳双功能化。该项研究成果发表在2026年3月10日出版的《德国应用化学》杂志上。

芳香族克莱森重排会瞬时产生去芳构化中间体，这类中间体通常极不稳定而难以捕获，因此会自发发生再芳构化。

研究组发现，这种看似必然的再芳构化过程可被有效抑制，从而实现不对称去芳构化双重官能团化。具体而言，他们开发了手性芳基亚砜的不对称脱水重排反应，该反应在极低温度（−95 °C）下进行，为原位捕获高度不稳定的去芳构化中间体提供了独特窗口。研究表明，多种亲核试剂（包括烯醇硅醚、有机锌试剂及杂原子亲核试剂）均可有效捕获这些中间体，生成具有最多四个连续立体中心的双重官能团化去芳构化产物。

值得注意的是，这些去芳构化产物可经历三种不同的脱硫转化途径，获得兼具轴手性和点手性的结构多样性手性产物。计算研究揭示了从传统再芳构化路径到本去芳构化体系的机制性转变，并阐明了连续手性传递过程中高保真性的起源。

附：英文原文

Title: Asymmetric Dearomative Dual-Functionalization via Rearomatization-Blocked Sulfonium Claisen Rearrangement

Author: Sheng Ye, Yanping Liu, Guoqing Liang, Yuchen Liang, Ling Zhu, Lichun Kong, Hanliang Zheng, Wenyao Wang, Bo Peng

Issue&Volume: 2026-03-10

Abstract: The aromatic Claisen rearrangement transiently generates dearomatized intermediates that are generally too unstable to be intercepted and thus undergo spontaneous rearomatization. In this study, we demonstrate that this otherwise inevitable rearomatization can be effectively suppressed, thereby enabling asymmetric dearomative dual functionalization. Specifically, we have developed an asymmetric dehydrative rearrangement of chiral aryl sulfimides that proceeds at exceptionally low temperature (95 °C), providing a unique window to intercept the highly unstable dearomatized intermediates in situ. A wide array of nucleophiles—including enol silyl ethers, organozinc reagents, and heteroatom nucleophiles—proved competent in capturing these intermediates, affording dual-functionalized dearomatization products with up to four contiguous stereocenters. Remarkably, these dearomatization products undergo three distinct desulfurization pathways, furnishing structurally diverse chiral products featuring both axial and point chirality. Computational studies reveal the mechanistic divergence from the conventional rearomatization pathway to the present dearomatization manifold and uncover the origin of the high fidelity in continuous chirality transfer.

DOI: 10.1002/anie.8953687

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.8953687