Detalle de: Forming Tertiary Organolithiums and Organocuprates from Nitrile Precursors and their Bimolecular Reactions with Carbon Electrophiles to Form Quaternary Carbon Stereocenters

Unstabilized tertiary organolithium intermediates are conveniently generated by reductive decyanation of nitriles, and these reagents and their derived cuprates couple in useful yields with carbon- centered electrophiles (see example). Chiral tertiary organolithium and organocuprate derivatives of substituted cis-perhydroazulenes and cis-perhydropentalenes react with electrophiles with high diastereoselectivity from the more-hindered concave face.