浙江大学李伟团队报道了Bench稳定的Meisenheimer复合物的合成、表征和发散反应性。相关研究成果于2024年10月30日发表在《美国化学会杂志》。

Meisenheimer配合物的化学性质在有机化学中具有重要意义。虽然硝基已被广泛用于促进Meisenheimer络合物的形成和稳定，但用户更友好的酯基的类似应用仍然是一个未探索的前沿。

该文中，研究人员报道了有显著的空气、水分和热稳定性的酯稳定的Meisenheimer配合物。

此外，可分离且定义明确的Meisenheimer中间体在脱芳烃反应中表现出不同的反应性，包括模块化1,4-加成、脱芳烃（2+3）环加成，甚至更高阶（4+n）环加合。

这些方法能够快速获得具有多个全碳四元中心，和有趣结构拓扑的复杂环己烷衍生物。

附：英文原文

Title: Bench-Stable Meisenheimer Complexes: Synthesis, Characterization, and Divergent Reactivity for Dearomatization

Author: Wei-Long Zeng, Qidong Xia, Chu-Qiao Li, Ming-Yang Wang, Wang-Ye Jin, Hanfeng Ding, Wei Li

Issue&Volume: October 30, 2024

Abstract: The chemistry of the Meisenheimer complexes is of fundamental interest in organic chemistry. While the nitro group has been extensively employed to facilitate the formation and stabilization of Meisenheimer complexes, the analogous application of more user-friendly ester groups has remained an unexplored frontier. Herein, we report ester-stabilized Meisenheimer complexes, which have remarkable air-, moisture-, and thermo-stability. Moreover, the isolable and well-defined Meisenheimer intermediates exhibit divergent reactivity for dearomatization reactions, including modular 1,4-additions, dearomative (2 + 3) cycloadditions, and even higher-order (4 + n) cycloadditions. These methodologies enabled rapid access to complicated cyclohexane derivatives with multiple all-carbon quaternary centers and interesting structure topologies.

DOI: 10.1021/jacs.4c12303

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c12303