3R-SUBSTITUTED AND NORBORNANE-ANNELATED 1H-PHOSPHOLANOXIDES: SYNTHESIS AND STRUCTURE

Tertiary phosphines, 1H-phosphines and 1H-phosphine oxides are widely used in organoelement and organometallic synthesis, hydrophosphinylation of alkenes and alkynes, as well as ligands and analogs of known biologically active compounds. Cyclic 1H-phosphine oxides are of practical interest as key monomers for the preparation of new reagents in organic synthesis and ligands of catalytic systems. However, in the literature there are a limited number of examples of the synthesis of cyclic 1H-phosphine oxides.
We have recently developed a one-pot method for the synthesis of alkyl(aryl)phospholanes and phospholenes in high yields, based on the in situ substitution reaction for aluminum atoms in aluminacyclopentanes by phosphorus atoms using alkyl(aryl)phosphorodichlorides. In the development of ongoing research on the development of effective methods for the synthesis of cyclic organophosphorus compounds, we have developed an effective one-pot method for the synthesis of new 3R-substituted and norbornane-annelated 1H-phospholanoxides by the reaction of substituted aluminacyclopentanes with phosphorus trihalide. Substituted aluminacyclopentanes were prepared in situ by the reaction of cycloaluminization of α-olefins and norbornene derivatives with triethylaluminum in the presence of bis(cyclopentadienyl)zirconium(IV) dichloride catalyst.
Thus, we have proposed an original one-pot method for the synthesis of 3R-substituted and norbornane-annelated 1H-phospholanoxides, which are of practical interest as precursors for obtaining catalysts for homogeneous catalysis.