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.