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.