One-Pot Sequential Alcohol Activation and Nickel-Catalyzed Cross-Electrophile Coupling with Chlorosilanes

A formal deoxygenative silylation of primary alcohols is reported. The one-pot procedure consists of an <i>in situ</i> bromination of the alcohol and a subsequent nickel-catalyzed cross-electrophile coupling of the formed alkyl bromide and various vinyl-substituted chlorosilanes. The key to success is the compatibility of the nickel catalysis as well as the chlorosilane electrophile with the byproducts of the preceding bromination step, especially with triphenylphosphine oxide likely acting as a weak ligand for the excess nickel catalyst used.