Scalable Synthesis of Vicinal Quaternary Stereocenters via the Solid-State Photodecarbonylation of a Crystalline Hexasubstituted Ketone

We report the synthesis and stereospecific solid-state photodecarbonylation of a hexasubstituted ketone featuring six distinct alpha-substituents. The photoproduct of the solid-state transformation features vicinal all-carbon quaternary stereocenters. While reactions carried out in bulk powders and aqueous crystalline suspensions were complicated by secondary photochemistry of the primary photoproduct, optimal conditions provided good yields and recyclable starting material. Subsequent transformations of the alpha-substituents having orthogonal chemical reactivity illustrate the potential of this transformation toward constructing complex architectures.