Most current processes for the general synthesis of primary amines by reductive amination are performed

with enormously excessive amounts of hazardous ammonia. It remains unclear how catalysts should be

designed to regulate amination reaction dynamics at a low ammonia-to-substrate ratio for the quantitative

synthesis of primary amines from the corresponding carbonyl compounds. Herein we show a facile

control of the reaction selectivity in the layered boron nitride supported ruthenium catalyzed reductive

amination reaction. Specifically, locating ruthenium to the edge surface of layered boron nitride leads to

an increased hydrogenation activity owing to the enhanced interfacial electronic effects between ruthenium

and the edge surface of boron nitride. This enables self-accelerated reductive amination reactions

which quantitatively synthesize structurally diverse primary amines by reductive amination of carbonyl

compounds with twofold ammonia.