Abstract: (PhO)3P·CH3I reacts with methyl-2,3-O-isopropylidene-L-rhamnopyranoside (I) to give a mixture of methyl-4,6-dideoxy-4-iodo-2,3-O-isopropylidene-α-L-mannopyranoside (II), methyl-5,6-dideoxy-5-iodo-2,3-O-isopropylidene-β-D-allofuranosi and methyl-5,6-dideoxy-5-iodo-2,3-O-isopropylidene-α-L-talofuranoside (IV) in the ratio of approx. 13:14:1. The course of substitution reactions at the iodine atoms in these compounds depends on nucleophilicity of the reagent used. Strong nucleophiles (e.g. PhCOSK) react with Walden inversion and without elimination. With the less nucleophilic NaN3 the reaction proceeds also with inversion, but hydrogen iodide elimination and pyranose ring contraction (in II) also take place to some extent. In the action of PhCOONa the formation of unsaturated monosaccharides is the predominant process, while the substitution of the iodine atom by the benzoyloxy group proceeds to a small extent and gives rise to a mixture of epimeric benzoates.

Cite: Kochetkov N.K. , Usov A.I. , Adamyants K.S.
Synthesis and nucleophilic substitution reactions of some iodo-deoxy sugars
Tetrahedron. 1971. V.27. N3. P.549-559. DOI: 10.1016/s0040-4020(01)90724-0 WOS OpenAlex

Identifiers:

Web of science:	WOS:A1971I870000005
OpenAlex:	W2008961725

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