Thermodynamically Controlled, Dynamic Binding of Diols to a 1,2-BN Cyclohexane Derivative

The reversible covalent binding of diols to an N-Bn 1,2-BN cyclohexane has been studied by 11B and 1H NMR spectroscopy and single-crystal X-ray diffraction analysis. The activation barrier for the reversible B–N Lewis acid–base interaction has been measured by variable-temperature NMR with bound (2R,3R)-(−)-2,3-butanediol (Tc = −40 °C, ΔG⧧ = 11.2 ± 0.2 kcal mol–1). Deuterium labeling experiments demonstrate that ligand exchange is reversible and rapid at room temperature, and competitive binding studies establish diol association as a thermodynamically controlled process.