Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity

Single-crystal structures of myo-inositol complexes with erbium ([Er₂(C₆H₁₁O₆)₂(H₂O)₅Cl₂]Cl₂(H₂O)₄, denoted ErI hereafter) and strontium (Sr(C₆H₁₂O₆)₂(H₂O)₂Cl₂, denoted SrI hereafter) are described. In ErI, deprotonation occurs on an OH of myo-inositol, although the complex is synthesized in an acidic solution, and the pK_a values of all of the OHs in myo-inositol are larger than 12. The deprotonated OH is involved in a μ₂-bridge. The polarization from two Er³⁺ ions activates the chemically relatively inert OH and promotes deprotonation. In the stable conformation of myo-inositol, there are five equatorial OHs and one axial OH. The deprotonation occurs on the only axial OH, suggesting that the deprotonation possesses characteristics of regioselectivity/chiral selectivity. Two Er³⁺ ions in the μ₂-bridge are stabilized by five-membered rings formed by chelating Er³⁺ with an O-C-C-O moiety. As revealed by the X-ray crystallography study, the absolute values of the O-C-C-O torsion angles decrease from ∼60 to ∼45° upon chelating. Since the O-C-C-O moiety is within a six-membered ring, the variation of the torsion angle may exert distortion of the chair conformation. Quantum chemistry calculation results indicate that an axial OH flanked by two equatorial OHs (double ax-eq motif) is favorable for the formation of a μ₂-bridge, accounting for the selectivity. The double ax-eq motif may be used in a rational design of high-performance catalysts where deprotonation with high regioselectivity/chiral selectivity is carried out.