Synthesis and Reactivity of Functionalized Arylcopper Compounds by Transmetalation of Organosilanes

Reactive organometallics are part and parcel of synthetic chemistry. Organosilanes potentially represent a cheap, robust, and environmentally benign precursor to reactive organometallics, but the nature of the very stable C-Si bond has generally prevented their use as precursors to more reactive organometallics. We present investigations into a copper fluoride complex which activates organosilanes in anhydrous media under mild conditions, effecting transmetalation to produce stable and isolable organocopper species containing sensitive functional groups including carbonyl groups, aryl bromides, benzylic chlorides, and alkyl ketones. This discovery allows us to better understand the fundamental reactivity of presumed intermediates in copper-catalyzed reactions and to develop new catalytic bond-forming processes of organosilane reagents.