ASYMMETRIC INDUCTION IN THE REACTION OF NONSYMMETRICAL PHOSPHINIC AND PHOSPHINOUS ACID CLORIDES WITH DERIVATIVES OF D-GLUCOFURANOSE

Abstract

Reaction of nonsymmetrically substituted chlorophosphines (1–3) with (−)-1,2:3,5-di-O-isopropylidene-α-D-glucofuranose (1) or (−)-1,2:5,6-di-O-cyclohexylidene-α-D-glucofuranose (5) proceeds with high stereoselectivity to give stereochemically pure phosphinic acid esters (6–8), which are starting compounds for the preparation of chiral organophosphorus compounds. Reaction of benzyl-phenylphosphinous acid chloride with (1) leads to optically pure phosphinous acid ester (9). The stereochemistry of the reaction is studied in dependence on the nature of the base, solvent, temperature and excess of chlorophosphine.

Key Words:

• Stereoselectivity
• 1,2:3,5-di-O-isopropylidene-α-D-glucofuranose (-)-1,2:5,6-di-O-cyclohexylidene-α-D-glucofuranose
• nonsymmetrical alkylarylchlorophosphines
• chiral phosphinic acid esters
• chiral phosphinous acid esters
• P-chiral compounds
• asymmetric synthesis