Zn-Mediated Fragmentation of Tertiary Alkyl Oxalates Enabling Formation of Alkylated and Arylated Quaternary Carbon Centers.

Zn-mediated reduction of readily accessible dialkyl oxalates derived from tertiary alcohols provides an efficient approach to C-O bond fragmentation and alkyl radical formation. With MgCl2 as the indispensable additive and Ni as the promoter, trapping the radical with activated alkenes and aryl-Ni intermediates allows for the generation of alkylated and arylated all-carbon quaternary centers.