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

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.