Recent Advances in Asymmetric Dearomatization of Nitro(hetero)arenes

Abstract

Asymmetric dearomatization reactions (CADA) have become fundamental chemical transformations in organic synthesis to rapidly assemble structurally diverse chiral carbocycles and heterocycles found in a plethora of bioactive molecules. Aromatic nitro compounds, which are readily available starting materials in both industrial and academic society, have been proved to be reactive towards various reaction partners, facilitating 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)arenes-enabled CADA, with a detailed discussion of diverse types of reactions, involving asymmetric cycloaddition, asymmetric Michael addition, and asymmetric interrupted Barton-Zard reaction. The reaction mechanisms, 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 exploratory research.