Recent advances in asymmetric dearomatization of nitro(hetero)arenes

Abstract

Catalytic asymmetric dearomatization reactions (CADA) have become fundamental chemical transformations in organic synthesis for the rapid assembly of structurally diverse chiral carbocycles and heterocycles found in a plethora of bioactive molecules. Aromatic nitro compounds, which are readily available starting materials used in both industry and academia, have been proved to be reactive with various reaction partners and can facilitate a range of asymmetric dearomatization reactions. Moreover, the nitro group in the products serves as a handle for further synthetic transformation, paving the way to valuable N-containing molecules. In this review, we systematically summarize recent advances in nitro(hetero)arene-enabled CADA, with a detailed discussion of a diverse variety of reactions, including asymmetric cycloadditions, asymmetric Michael additions, and the asymmetric interrupted Barton–Zard reaction. The reaction mechanism, substrate scope, and practical applications of these transformations are comprehensively analyzed. Finally, we offer insights into the current limitations of this field, which are expected to inspire further investigations.