Breaking Aromaticity with Aminocatalysis: A Convenient Strategy for Asymmetric Synthesis

Since the turn of the millennium, catalytic reactions promoted by primary or secondary amines have emerged as a highly useful method for organic chemistry. Very recently, the potential of such synthetic strategies has been vastly expanded by incorporating the principle of aromaticity breaking. Novel reaction pathways can now be accessed through the intermediacy of polyenamine intermediates derived from (hetero)aromatic systems. The proper design of carbonyl starting materials, combined with the high stereochemical efficiency provided by well‐established aminocatalysts, has enabled the synthesis of products with (hetero)aromatic frameworks in highly enantio‐ and diastereomerically enriched form. In this Minireview, we provide an overview of recent advances in this field of research and familiarize the reader with new synthetic opportunities offered by these interesting methodologies.