functional group tolerance

substrate scope

hydroboration

n-heterocyclic carbene

borylation

aromatic substitution

protocol synthesis

Bulletin of the Chemical Society of Japan

This account highlights the development of efficient borylation reactions of arenes toward organoboron-based materials. Upon the introduction of boron substituents, an intramolecular tandem bora-Friedel–Crafts reaction (tandem electrophilic C–H borylation of arenes) takes place with the appropriate choices of boron source, Lewis acid, Brønsted base, and reaction temperature to construct polycyclic frameworks with ring-junction boron atoms in a one-pot manner. Notably, electron-rich arenes, such as triarylamines, undergo one-shot multiple (up to quadruple) borylations with boron trihalides through successive inter- and intramolecular processes. The borylated compounds exhibit attractive optoelectronic properties and substantial stabilities in practical applications. These reactions are efficient, facile, scalable, and free from precious reagents, and will thus pave the way for the development of next-generation optoelectronic materials.

Development of One-Shot/One-Pot Borylation Reactions toward Organoboron-Based Materials