Glycosyl phosphorodithioates

Borowiecka J, Lipka P, Michalska M (1988) Stereoselective synthesis of S-(2-deoxy-a-D-glycosyl) phosphorodithioates and of their (2R)-2-deoxy-2-deuterio analogs. Novel route to C-2 deuterium labeled 2-deoxymonosaccharides. Tetrahedron 44 2067-2076... 

Glycosyl phosphorodithioates 171 (Scheme 46), prepared by action of 0,0-dialkylphosphorodithioic acid on the corresponding glycals, were employed as glycosyl donors in the synthesis of 2-deoxydisaccharides. The glycosylations of primary and secondary acceptors in the presence of silver fluoride proceeded sluggishly (from 7 to 12 days) and the a-stereoselectivities were somewhat low, except in a few cases [151]. 

Scheme 46. Glycosyl phosphorodithioates (171), glycosyl phosphorothioates (172) and glycosyl phosphoroselenoates (173).

Scheme 5.55 Conversion of glycals to phosphorodithioates as glycosyl donors.

H. Bielawska and M. Michalska, 2-Deoxyglycosyl phosphorodithioates. A novel type of glycosyl donors. Efficient synthesis of 2 -deoxydisaccharides, J. Carbohydr. Chem., 10 (1991) 107-112. 

Deuterioglycosides. 0,0-Dimethyl-S-(3,4,6-tri-0-acetyl-2(R)-2-deoxy-2-deuterio-a-D-arabinohexopyranosyl)phosphorodithioate added to Na in methanol at — 15°, the mixture allowed to react at this temp, for 2 h and at 20° for 1 h, concentrated, and treated with acetic anhydride in pyridine methyl 3,4,6-tri-0-acetyl-2(R)-2-deoxy-2-deuterio-P-D-arabinohexopyranoside. Y 70%. F.e.s. J. Borowiecka et al.. Tetrahedron 44, 2067-76 (1988) review of glycosyl thio-, seleno-, and telluro-phosphates s. Heterocycles 28, 1249-56 (1989). 

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