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.