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The thio-Mitsunobu reaction: a useful tool for the preparation of 2,5-anhydro-2-thio- and 3,5-anhydro-3-thiopentofuranosides.
- Source :
-
Carbohydrate research [Carbohydr Res] 2004 Jul 12; Vol. 339 (10), pp. 1787-802. - Publication Year :
- 2004
-
Abstract
- The unprotected methyl L-arabinofuranosides, D-ribofuranosides and D-xylofuranosides are transformed into the corresponding S-acetyl-5-thio derivatives by the thio-Mitsunobu reaction. Mesylation and subsequent reaction with sodium hydrogen carbonate led, depending on the configuration of the intermediate, to 2,5-anhydro-2-thio- or 3,5-anhydro-3-thiopentofuranosides. Due to inversion at C-3 or C-2 during the intramolecular nucleophilic displacement the products exhibit L-lyxo-, D-arabino- or D-lyxo-configuration. Analogously, the methyl 2,3-anhydro-D-ribofuranosides yielded 5-thio-S-acetates with intact 2,3-oxirane groups, which were cyclised with sodium hydrogen carbonate by epoxide ring opening and concomitant ring closure to form exclusively 3,5-anhydro-3-thio-D-xylofuranosides. A related 3,5-anhydro-3-seleno-D-lyxofuranoside was obtained by reaction of a 3,5-di-O-mesyl-D-arabinofuranoside with sodium hydrogen selenide. Several X-ray diffraction analyses proved the structures of the products.
- Subjects :
- Acetates chemistry
Bicarbonates chemistry
Biochemical Phenomena
Biochemistry
Crystallography, X-Ray
Furans chemistry
Hydrogen chemistry
Magnetic Resonance Spectroscopy
Models, Chemical
Models, Molecular
Selenic Acid
Selenium Compounds chemistry
Sodium chemistry
X-Ray Diffraction
Xylose chemistry
Arabinose chemistry
Subjects
Details
- Language :
- English
- ISSN :
- 0008-6215
- Volume :
- 339
- Issue :
- 10
- Database :
- MEDLINE
- Journal :
- Carbohydrate research
- Publication Type :
- Academic Journal
- Accession number :
- 15220089
- Full Text :
- https://doi.org/10.1016/j.carres.2004.04.020