Pd-Catalyzed, Highly Selective C(sp(2))-Br Bond Coupling Reactions of o-(or m-, or p-) Chloromethyl Bromobenzene with Arylboronic Acids

Highly selective C(sp(2))–C(sp(2)) cross-coupling of dihalogenated hydrocarbons comprising C(sp(2))–Br and C(sp(3))–Cl bonds with arylboronic acids is reported. This highly selective coupling reaction of the C(sp(2))–Br bond is successfully achieved using Pd(OAc)(2) and PCy(3)·HBF(4) as the palladium source and ligand, respectively. A series of chloromethyl-1,1′-biphenyl compounds are obtained in moderate-to-excellent yields. Moreover, this protocol can be extended to the one-pot dual arylation of 1-bromo-4-(chloromethyl)benzene with two arylboronic acids, leading to diverse unsymmetrical 4-benzyl-1,1′-biphenyl derivatives.