Synthesis and characterization of a pair of O-/O- 12-P-6 alkyloxaphosphates with a P-O-C-C four-membered ring.

Structurally characterized hexacoordinate organophosphorus compounds remain rare due to their highly reactive nature and thermal instability. Herein we report the first synthesis of a pair of O-facial and O-meridional hexacoordinate oxaphosphates ( and ) obtained from the O-apical and O-equatorial β-hydroxyalkylphosphoranes and . This was achieved by using the bulky CF-groups on the ortho-substituted aryl backbone. Calculations of the relative energies of possible isomers indicate and are thermodynamic products. Although the mechanisms of their formation and the determining factor of stereo-selectivity are still unclear, their isolation and structure conformation contributes to a formulation of a viable strategy for diastereoselective synthesis of heteroleptic hexacoordinate organophosphates.