Silyloxymethylation of Aryl Halides via Metallaphotoredox Catalyzed Desulfinative Cross-Coupling with Silyl Rongalite

A visible-light-triggered silyloxymethylation of aryl halides has been developed by the merger of photoredox and transition metal catalysis. Under the Ru/Ni dual catalytic conditions, sodium tert-butyl-dimethylsilyloxymethanesulfinate (SOMS) undergoes facile extrusion of sulfur dioxide to engender a silyloxymethyl radical that engages in the cross-coupling with a range of aryl halides to produce benzyl silyl ether derivatives. The protocol is also effective with alkenyl halides and triflates, thus offering an efficient synthetic approach to the silyl-protected allylic alcohols. A photocatalytic silyloxymethylation of aryl halides has been developed via the merger of photoredox and transition metal catalysis. Sodium tert-butyldimethylsilyloxymethanesulfinate serves as an effective progenitor of a silyloxymethyl radical with extrusion of SO2. The Ru/Ni dual catalytic protocol enables an efficient cross-coupling for the generic synthesis of benzylic silyl ether derivatives.+image