Although transition-metal-catalyzed C–C bond activation has been investigated extensively, C–C bond cleavage manipulated by hydrogen transfer has been unexplored. In this work, we disclose a skeleton reorganization of alkene-tethered benzocyclobutenols through Rh-catalyzed C–C bond cleavage coupled with intra- and intermolecular hydrogen transfer. The reaction pathway was well-tuned by the catalytic systems. As a result, divergent benzofurans bearing 4-β-hydroxy or 4-β-keto moieties were synthesized under pH- and redox-neutral conditions.

The transition-metal-catalyzed intramolecular hydroarylation of alkenes has been recognized as a straightforward approach for the construction of 3,3-disubstituted 2,3-dihydrobenzofurans. The reactions mainly rely on the reductive Heck reaction of aryl halides or the direct C−H bond activation of arenes bearing a directing group. This work realizes the Rh-catalyzed intramolecular hydroarylation of olefin-tethered benzocyclobutenols via C−C bond activation, which offers an alternative approach to 3,3-disubstituted 2,3-dihydrobenzofurans bearing a 4-β-keto moiety. The methodology features 100% atom economy and pH-and redox-neutral conditions, and is applicable to the late-stage functionalization of complex molecules. The asymmetric variant has also been achieved with excellent enantioselectivities.