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  4. Enantiomerically Pure 7-Oxabicyclo[2.2.1]Hept-5-En-2-Yl Derivatives (Naked Sugars) as Synthetic Intermediates .17. Total, Asymmetric-Synthesis of Hexoses and Azasugars Branched at C(5)
 
research article

Enantiomerically Pure 7-Oxabicyclo[2.2.1]Hept-5-En-2-Yl Derivatives (Naked Sugars) as Synthetic Intermediates .17. Total, Asymmetric-Synthesis of Hexoses and Azasugars Branched at C(5)

Wagner, J.
•
Vogel, P.  
1991
Tetrahedron

The Diels-Alder adduct (-)-5 (a "naked sugar") of furan to 1-cyanovinyl (1R')-camphanate was converted into (+)-(1R,5S,6S,7S)-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicylo[3.2. 1]octan-3-one and into (+)-(1R,5S,6S,7S)-7-endo-(benzyloxy)-6-exo-{[(t-butyl)dimethylsilyl]oxy} -2,8-dioxabicyclo[3.2.1]-octan-3-one ((+)-17). Double methylation at C(4) gave the corresponding 5-deoxy-5-C-dimethyl furanurono-6,1-lactones (+)-42 and (+)-19, respectively. Stereoselective and successive methylation and benzyloxymethylation of (+)-(1R,5S,6S,7S)-6-exo,-7-exo-(isopropylidenedioxy)2,8-dioxabicyclo[3.2 .1]octan-3-one gave (+)-(1R,4R,5S,6S,7S)4-exo-[(benzyloxy)methyl]-6-exo,7-exo-(isopropyliden edioxy)-4-endo-methyl-2,8-dioxabicyclo[3.2.1]octan-3-one ((+)-9). Highly stereoselective oxydative decarboxylation of lactones (+)-9 and (+)-19 led to 5-C-methyl-alpha-beta-D-talo-hexose ((-)-1) and to 6-deoxy-5-C-methyl-alpha-beta-L-arabino-hexose ((-)-2), respectively. Transformation of lactones (+)-9 and (+)-42 into the corresponding acyl azides and their Curtius rearrangements led to (5-ammonio-1,5-N-anhydro-5-deoxy-5-C-methyl-alpha-beta-D-talo-hexitol)-1 -sulfonate ((+)-3) and to (5-ammonio-1,5-N-anhydro-5,6-dideoxy-5-C-methyl-alpha-beta-L-ribo-hexito l)1-sulfonate ((+)-4), respectively.

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Type
research article
DOI
10.1016/S0040-4020(01)91030-0
Author(s)
Wagner, J.
Vogel, P.  
Date Issued

1991

Published in
Tetrahedron
Volume

47

Issue

46

Start page

9641

End page

9658

Subjects

C bond formation

•

radical cyclization reactions

•

n-acetylneuraminic

•

acid

•

diels-alder reactions

•

stereoselective synthesis

•

chain sugars

•

pyranosidic homologation

•

dipyranoside precursors

•

absolute-configuration

•

glucosidase-inhibitors

Note

Univ lausanne,chim sect,2 rue barre,ch-1005 lausanne,switzerland.

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LGSA  
Available on Infoscience
November 9, 2005
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/219651
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