Ir-Catalyzed Selective B(3)-H Amination of o-Carboranes with NH3

Ammonia gas, NH3, is a cheap and widely used industrial feedstock, which has received tremendous research interests in its functionalization. This work reports a breakthrough in catalytic selective cage B(3)-H amination of o-carboranes with NH3 via Ir-catalyzed B-H/N-H dehydrocoupling, offering convenient and efficient access to a series of 3-NH2-o-carborane derivatives in moderate to high isolated yields with a broad substrate scope. The employment of readily available NH3 gas as the aminating reagent with H-2 as the sole byproduct endows the protocol economy, practicability, and environmental friendliness. A plausible reaction mechanism is proposed on the basis of control experiments.

Automated summary

This study presents a new method for the selective amination of o-carboranes with NH3 gas via Ir catalysis, providing a convenient and efficient access to a series of 3-NH2-o-carborane derivatives. The use of NH3 gas as the amination reagent with H2 as the sole byproduct makes the protocol economical, practical, and environmentally friendly.