| Abstract: | The intramolecular coupling of two C(sp3)?H bonds to forge a C(sp3)?C(sp3) bond is enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)?C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C?Br bond acting as an internal oxidant. Furthermore, it allows the coupling between two moderately acidic primary or secondary C?H bonds, which are adjacent to an oxygen or nitrogen atom on one side, and benzylic or adjacent to a carbonyl group on the other side. A variety of valuable fused heterocycles were obtained from easily accessible ortho‐bromophenol and aniline precursors. The second C?H bond cleavage was successfully replaced with carbonyl insertion to generate other types of C(sp3)‐C(sp3) bonds. |
