Palladium-catalyzed Negishi cross-coupling of 3-bromo-1-(tert-butyldimethylsilyl)-1,2-dihydro-1,2-azaborine while maintaining the B-H functionality has been demonstrated. 17 examples, including dialkylzinc, alkyl-, alkenyl-, aryl-, as well as nitrogen-, sulfur-, and oxygen-containing heteroaryl-zinc halide reagents have been coupled to generate new C(3) substituted 1,2-azaborines in moderate to excellent yields.