LAUSR

Benzoisoxazoles, with a distinctive 10‐π‐electron system and significant polarity, readily trigger N‐O bond cleavage, enabling multifaceted applications in organic synthesis. Over the past decade, the exponentially increased use of benzoisoxazoles towards the synthesis of highly valuable N‐containing scaffolds, especially N‐heterocycles, has garnered substantial attention. In this review, we summarize recent developments in the transformation of 2,1‐ and 1,2‐benzoisoxazoles since 2015, highlighting the neglected resemblances of these two nitroxy heterocycles. Key processes in the assorted reactions of benzoisoxazoles, including mechanisms, scope, catalyst‐controlled chemodivergence, current limitations, and developmental prospects, are also introduced and discussed.