Zeng Wei-Long, Xia Qidong, Li Chu-Qiao, Wang Ming-Yang, Jin Wang-Ye, Ding Hanfeng, Li Wei
Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Am Chem Soc. 2024 Nov 13;146(45):30764-30770. doi: 10.1021/jacs.4c12303. Epub 2024 Oct 30.
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 + ) cycloadditions. These methodologies enabled rapid access to complicated cyclohexane derivatives with multiple all-carbon quaternary centers and interesting structure topologies.
迈森海默络合物的化学性质在有机化学中具有根本重要性。虽然硝基已被广泛用于促进迈森海默络合物的形成和稳定，但更具用户友好性的酯基的类似应用仍是一个未被探索的领域。在此，我们报道了酯稳定的迈森海默络合物，它们具有显著的空气稳定性、湿气稳定性和热稳定性。此外，可分离且明确的迈森海默中间体在脱芳构化反应中表现出不同的反应性，包括模块化的1,4-加成、脱芳构化(2 + 3)环加成，甚至高阶(4 + )环加成。这些方法能够快速获得具有多个全碳季中心和有趣结构拓扑的复杂环己烷衍生物。
