Rhodium-catalyzed insertion of nitrenes into B–H bonds

The paper presents a new method for the formation of B-N bond by the catalytic insertion of nitrenes into organic boranes. The reaction proceeds most selectively for cyclic boranes with 2-phenylpyridine framework and nitrenes generated in situ by oxidation sulfonamides and sulfamates. The most effective catalysts for the process are rhodium and ruthenium carboxylates of [M2(OOCR)4]X type. Complexes with NTTL ligands derived from S-tert-leucine provide chiral products with stereogenic boron atoms. The developed approach can be useful for the introduction of boron heterocycles into functional materials and biologically active molecules.