1 -deoxy-1 -nitrosugar

Mirza, S., and Vasella, A., Deoxy-nitrosugars. Part J. Synthesis of methyl shikimate and of diethyl phosphashikimalc from D-ribose, Helv. Chim. Acta, 67, 1562, 1984. 

Aebischer B, Hollenstein R, Vasella A (1983) 168. Deoxy-nitrosugars. The anomeric effect of the nitro group. Helv Chim Acta 66 1748-1754... 

Anomeric triphenylphosphonium salts have been used as well as phenylsul-fides,but in the latter case extra stabilization is necessary (see below). Anomeric nitrosugars, which have been extensively studied in C-glycosylation reactions by Vasella, will be covered in Sect. 2.2.1 and ester enolates derived from 3-deoxy-2-ketoulosonic acids (sialic acid and KDO derivatives), which bear a structural similarity to 2-deoxy pyranosides, will be covered in Sect. 4.4. Deprotonation of anomeric phenylsulfones has been discussed in Sect. 2.1.1 and additional transformations on closely related compounds are presented in Scheme 14 [20]. Alkylation of phenylsulfone 54 with epoxide 55 provides adduct 56 which eliminates benzenesulfinic acid at room temperature to give the C(l)-alkylated glycal 57 a similar elimination is also observed with adducts derived from... 

Related to nitroalkylsugars are 1-deoxy-l-nitrosugars. These compounds are relatively easy to prepare via oximes. As shown in Scheme 7.37, Vasella et al. [139,140] effected this transformation via addition of an aldehyde to the oxime, shown. Subsequent treatment with ozone gave an anomeric mixture of the desired 1-deoxy-l-nitrosugar in a 73% overall yield. 

The utility of 1-deoxy-l-nitrosugars was further demonstrated by Vasella et al. [141] in a study of nitroalkylation reactions. Summarized in Scheme 7.38, the study involved the addition of nitromethane and 2-nitropropane. The reactions gave an excess of 70% yield. 

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