Rhodium(III)-Catalyzed Chemo-divergent Couplings of Sulfoxonium Ylides with Oxa/azabicyclic Olefins.

Rh(III)-catalyzed C-H functionalization of sulfoxonium ylides has been realized in chemo-divergent couplings with oxa/azabicyclic olefins. Divergent [4 + 2] annulation and C-H alkylation have been attained under controlled condition. In the annulation system, sulfoxonium ylide functions as a traceless oxidizing directing group. In contrast, the introduction of PivOH shunted the selectivity to ring-retentive alkylation.