Copper-Catalyzed Enantioselective and Exo-Selective Addition of Silicon Nucleophiles to 7-Oxa- and 7-Azabenzonorbornadiene Derivatives.

An enantioselective formal hydrosilylation of 7-oxa- and 7-azabenzonorbornadiene derivatives is reported. The exo-selective addition of the silicon moiety across these strained alkenes is achieved under copper catalysis, employing Si-B reagents as silicon pronucleophiles in the presence of an alkoxide base. No ring opening is observed. While successful for those substrates, the same procedure cannot be applied to benzonorbornadiene, norbornadiene, or norbornene.