Highly Enantioselective Rh-Catalyzed Carboacylation of Olefins: Efficient Syntheses of Chiral Poly-Fused Rings

Here we report the first highly enantioselective Rh-catalyzed carboacylation of olefins via C–C bond activation of benzocyclobutenones. Good yields and excellent enantioselectivities (92–99% ee, 14 examples) were obtained for substrates with various steric and electronic properties. In addition, fully saturated poly-fused rings were prepared from the carboacylation products through a challenging catalytic reductive dearomatization approach. These investigations provide a distinct way to prepare chiral carbon frameworks that are nontrivial to access with conventional methods.