Electrophilic C–H Borylation and Related Reactions of B–H Boron Cations

Catalytic
procedures are described for the amine-directed borylation
of aliphatic and aromatic tertiary amine–boranes. Sequential
double borylation is observed in cases where two or more C–H
bonds are available that allow 5-center or 6-center intramolecular
borylation. The HNTf2-catalyzed borylation of benzylamine–boranes
provides a practical means for the synthesis of ortho-substituted
arylboronic acid derivatives, suitable for Suzuki–Miyaura cross-coupling
applications.