Photochemical Dearomative Skeletal Modifications of Heteroaromatics

Dearomatization has emerged as a powerful manifold for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field has evolved beyond the simple dearomatization driven by new synthetic technology development. With the renaissance of photocatalysis and expanding the activation mode, the last few years have witnessed impressive developments on innovative photochemical dearomatization methodologies, enabling skeletal modifications of the dearomatic structures. They offer truly efficient and useful tools for facile construction of highly complex structures in synthesis of nature products and drug discovery. In this review, we aim to provide a mechanistically insightful overview on these innovations based on the degree of skeletal alternation, categorized into dearomative functionalization and skeletal editing, and highlight their synthetic utilities.