High‐yield access to long‐sought 1,8‐bis[pinacolato(boryl)]naphthalene

Abstract

AbstractDespite their apparent simplicity and numerous potential applications, 1,8‐bis(boronic ester) derivatives of naphthalene, 1,8‐C10H6[B(OR)2]2, have remained elusive until today. We now disclose a facile access route to this compound class via alkoholysis of the 1,8‐naphthalenediyl‐bridged diborane(6) 1. In the cases of monotopic MeOH or EtOH, the target compounds 1,8‐C10H6[B(OR)2]2 (R=Me (2), Et (4)) are contaminated with about 10 % of the corresponding mixed boronic ester/anhydride. By using ditopic pinacol (pin) or 1,8‐naphthalenediol (ndl), the formation of the undesired side products is suppressed and 1,8‐C10H6(Bpin)2 (6) can be isolated in 80 % yield (due to solubility issues, the yield of 1,8‐C10H6(Bndl)2 (7) is lower and less reproducible). The bis(boronic ester)s 2, 4, 6, and 7 have been structurally characterized by X‐ray diffraction. 6 has a sterically encumbered, remarkably distorted molecular framework with a torsion angle B−C(ipso)−C’(ipso)−B’ of 38.63(9)°.