Reaction of trialkylboranes with organic azides in refluxing xylene, followed by hydrolysis, leads to good yields of secondary amines. This reaction is highly dependent on the steric effects around both boron and the azide moiety. The reaction becomes much slower when the steric bulk of one of the reagents is increased and fails when both are hindered. The dialkylchloroboranes are more reactive than trialkylboranes and provide better yields of the desired secondary amines with a11 azides tested. The alkyldichloroboranes react with organic azides at temperatures between room temperature and 60°C and produce excellent yields of secondary amines. Furthermore, the stereochemistry of the original carbon-boron bond is retained. The mechanism of these reactions is discussed and the reaction applied to the synthesis of N-alkyl- and N-arylaziridines. © 1987.
Brown, H. C., Midland, M. M., Levy, A. B., Brown, H. C., Wetherill, R. B., Suzuki, A., … Itoh, M. (1987). Organoboranes for synthesis. Reaction of organoboranes with representative organic azides. A general stereospecific synthesis of secondary amines and N-substituted aziridines. Tetrahedron, 43(18), 4079–4088. https://doi.org/10.1016/S0040-4020(01)83446-3