Transition metal-free B(dan)-installing reaction (dan: naphthalene-1,8-diaminato): H-B(dan) as a B(dan) electrophile.

H-B(dan) was demonstrated to serve as a B(dan) electrophile, despite its highly diminished boron-Lewis acidity, leading to direct and transition metal-free approach to R-B(dan) of high synthetic utility upon treatment with Grignard reagents. Iterative cross-coupling of 5-bromo-2-pyridyl-B(dan), synthesized by the present method, was also achieved.

B(MIDA)-Containing Diborons.

Unsymmetrical B(MIDA)-containing diborons of potential synthetic utility were found to be synthesized from the readily available (neop)B-B(neop) and (HO)2B-B(OH)2, and the procedure was extended to the generation of symmetrical (MIDA)B-B(MIDA). NMR and X-ray crystal structure studies revealed that B(MIDA) units of all of the diborons obtained in this study were in rigid tetrahedral environment.