Sugar phosphine oxide

Tronchet, J.M.J., Neeser, J.-R., and Charollais, E.J., Some sugar phosphates, phosphonates and phosphine oxides. Preliminary communication, Helv. Chim. Acta, 61, 1942, 1978. 

The synthesis of chiral phosphine oxides has stimulated effort in a number of laboratories in recent years. An elegant new approach to the problem involves the use of sugar-derived phosphorus heterocycles. These are 1,3,2-dioxa-phosphorinan-2-ones, such as (1), formed from glucosides and various phosphonic dihalides, such as (2). The preparation of chiral phosphine oxides... 

Recently we have proposed a convenient synthesis of phosphorus analogs of sucrose. Di-chloro-perbenzylated derivative 27 (an intermediate in the synthesis of 22 via route c in Scheme 5), upon reaction with Ph2P anion, provided sucrose di-phosphine 28. However, regardless of the conditions, this compound was always oxidized to phosphine oxide 29. This is rather surprising, since such type of phosphines derived from simple sugars are relatively resistant towards oxidation (Scheme 6). 

Two sets of branched-chain sugar phosphonates, having the phosphonate attached to the C-3 branch carbon, have been synthesized, one such set being Illustrated in Scheme 3, and a variety of compounds of this type and related phosphinates and phosphine oxides... 

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