Deoxygenated sugars synthesis

Recently, some knowledge was acquired concerning nature s approach to the synthesis of dideoxy sugars. 6-Deoxygenation of glucose seems to follow a redox pathway via the nucleotide glucoside dTDP-glucose with oxidoreductase which leads to a 6-deoxy-4-uloside [1],... 

J. R. Rasmussen, C. J. Slinger, R. J. Kordish, and D. D. Newman-Evans, Synthesis of deoxy sugars. Deoxygenation by treatment with AV -thiocarbonyldiimidazole/tri-n-butylstannane, J. Org. Chem., 46 (1981) 4843-4846. 

However, it is rather difficult to search a library of natural sugars for an appropriate sugar derivative for the synthesis of 30. It is necessary to find either 5-deoxy-L-arabinose (61) or 5-deoxy-L-ribose (62), neither of which is available from natural resources [69]. Chemical derivation from easily available sugars is the only way to obtain 61 and 62,however, simple deoxygenation of the terminal alcohol group from L-arabinose (63) and L-ribose (64) generally requires a multi-step process. For example, the deoxygenative transformation... 

The reduction of halides or sulfonates is one of the most conventional methods for the synthesis of deoxy sugars. This method is particularly useful for the deoxygenation of primary hydroxyls of carbohydrates. Reduction has been accomplished employing one of the following three methods. 

Haskell, T H, Woo, P W K, Watson, D R, Synthesis of deoxy sugar. Deoxygenation of an alcohol utilizing a facile nucleophilic displacement step, J. Org. Chem., 42, 1302-1305, 1977. 

Application of the preceding strategy to multistriatin synthesis (Scheme 11.26) started with compound 7, which was deoxygenated at C3 and further elaborated to ketone 106 [49]. Wittig methylenation provided 107, and subsequent double bond reduction using Wilkinson s catalyst afforded the dimethylated compound 34 [93]. Further manipulation yielded a-multistriatin 108, the pheromone of Scolytus multistriatus. Other syntheses of this pheromon from sugars have been reported [48,94,95]. 

Danishefsky diene, 619 L-Daunosamine, 597 total synthesis, 601 Deoxy sugars, 151 Deoxygenation, 151... 

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