Diarylmethanes through an Unprecedented Palladium‐Catalyzed C−C Cross‐Coupling of 1‐(Aryl)methoxy‐1 H ‐Benzotriazoles with Arylboronic Acids

1‐(Aryl)methoxy‐1 H ‐benzotriazoles (ArCH 2 OBt) are bench‐stable reagents that are prepared readily from 1 H ‐benzotriazol‐1‐yl‐4‐methylbenzenesulfonate and benzylic alcohols. These compounds, which contain a N−O−C bond, undergo cross‐coupling with arylboronic acids by C−O bond scission with catalysts that comprise Pd(OAc) 2 and biarylphosphine ligands. Such reactivity of ArCH 2 OBt derivatives, which lead to diarylmethanes, has not been described previously and constitutes a new activation of benzylic alcohols. With regard to the various ligand‐metal complexes that support catalytic activity, it appears that those with smaller “percent buried volumes” (% V bur ) provide better outcomes. This factor has been evaluated in the initial optimization studies and in further reactions with difficult coupling partners. Ligand electronics of the biaryl moiety seem to play a lesser role in this type of reaction. The biscoordinating bis[(2‐diphenylphosphino)phenyl] ether appears to be suitable to improve the yields of low‐yielding reactions.