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.