Synthesis and structural analysis of higher analogs of sucrose

Article abstract of DOI:10.1080/07328300008544111

Three sucrose monoalcohols with free hydroxyl groups at C-1', C-6, and C-6' (1, 4, and 6) were prepared selectively and in good yield from 2,3,3',4,4'-penta-O-benzylsucrose. These compounds were oxidized to aldehydes and reacted with stabilized ylide, Ph₃P=CHCO₂Me to afford appropriate α,β-unsaturated esters 10, 11, and 12. Each olefin was cis-hydroxylated with OsO₄/NMO to stereoisomeric diols 13/14, 15/16, and 17/18, configurations of which were assigned by chemical correlation and CD evaluation. Stereoselectivity of the osmylation reaction was surprisingly low (ca 3:2), especially as compared to a similar process performed on simple derivatives of 6,7-unsaturated methyl glycosides for which the ratio of isomeric diols was assigned as 10:1. The osmylation of 11 (derivative homologated by a C₂-unit at the glucose part) did not obey Kishi's rule. Horner-Emmons reaction of sucrose aldehyde 7 with a sugar-derived phosphonate 22 afforded α,β-unsaturated derivative 24, homologated by a C₇-unit at the glucose end.

Full text of DOI:10.1080/07328300008544111

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Journal of Carbohydrate Chemistry
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Synthesis and Structural Analysis of
Higher Analogs of Sucrose
Slawomir Jarosz , Mateusz Mach & Jadwiga Frelek
a Institute of Organic Chemistry, Polish Academy of Sciences
ul. Kasprzaka , 44, 01-224 Warszawa, Poland E-mail:
b Institute of Organic Chemistry, Polish Academy of Sciences
ul. Kasprzaka , 44, 01-224 Warszawa, Poland E-mail:
c Institute of Organic Chemistry, Polish Academy of Sciences
ul. Kasprzaka , 44, 01-224 Warszawa, Poland E-mail:
Published online: 27 Feb 2008.
To cite this article: Slawomir Jarosz , Mateusz Mach & Jadwiga Frelek (2000) Synthesis and
Structural Analysis of Higher Analogs of Sucrose, Journal of Carbohydrate Chemistry, 19:6,
693-715, DOI: 10.1080/07328300008544111
To link to this article: http://dx.doi.org/10.1080/07328300008544111
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