Carbohydrates Wittig synthesis

To summarize, unstabilized carbohydrate phosphoranes are useful entities for the synthesis of long-chain carbohydrates by a Wittig process as long as the proper experimental conditions are employed and as long as the 6-oxygen is attached by another set of bonds to... 

N. K. Kochetkov, B. A. Dmitriev, and L. V. Backinowsky, Application of the Wittig reaction to the synthesis of 3-deoxy-D-manno-octulosonic acid, Carbohydr. Res., 11 (1969) 193-197. 

Grindley, T B, Wickramage, C, A novel approach to the synthesis of C-glycosyl compounds the Wittig rearrangement, J. Carbohydr. Chem., 1, 661-685, 1988. 

Nicotra, F, Panza, L, Ronchetti, F, Russo, G, Toma, L, Synthesis of C-glycosyl compounds by the Wittig iodocyclization procedure. Differences from mercuriocyclization, Carbohydr. Res., 171, 49-57, 1987. 

Sin, N and Kallmerten, J, Diastereoselective [2,3] Wittig rearrangement of carbohydrate-derived tertiary aUylic ethers. 2. Synthesis of an advanced rapamycin intermediate from D-glucose, Tetrahedron Lett., 34, 753-756, 1993. 

For a review, see Jarosz, S, Synthesis of higher carbon sugars via coupling of simple monosaccharides — Wittig, Homer-Emmons, and related methods, J. Carbohydr. Chem., 20, 93-107, 2001. 

A general synthesis for all diastereomeric L-hexoses, as an example for monosaccharides that often do not occur in the chiral pool, has been worked out. The epoxidation of allylic alcohols with tertiary butyl hydroperoxide in presence of titanyl tartaric ester catalysts converts the carbon-carbon double bond stereose-lectively to a diol and is thus ideally suited for the preparation of carbohydrates. The procedure is particularly useful as a repetitive two-carbon homologiza-tion in total syntheses of higher monosaccharides and other poly hydroxy compounds. It starts with a Wittig reaction of a benzylated a-hydroxy aldehyde with (triphenylphosphoran-ylidene)acetaldehyde to produce the olefinic double bond needed for epoxidation. Reduction with sodium-borohydride... 

J. M. Garcia Fernandez, C. O. Mellet, V. M. Diaz Perez, J. Fuentes, J. Kovacs, and I. Pinter, Synthesis of (1 -6)-carbodiimide-tethered pseudo oligosaccharides via aza-Wittig reaction, Carbohydr. Res, 304 (1997) 261-270. 

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