Substrate‐Controlled Divergent Oxidative Transformations of Rigid Indene Scaffolds

A substrate‐controlled strategy for oxidative transformations of strained indene scaffolds by meta‐chloroperoxybenzoic acid (m‐CPBA), achieving divergent pathways of dicarbonylative cleavage and oxidative migration of double bonds, was developed. When dihydroindeno‐indenes featuring high ring strain were employed as substrates, sequential epoxidation/epoxide opening followed by oxidative C─C bond cleavage successfully afforded indanone‐based 1,5‐dicarbonyl compounds. In contrast, comparatively flexible 3,3‐disubstituted indenes preferentially underwent oxidative migration over C─C bond cleavage, enabling efficient construction of indanones featuring quaternary carbon centers.