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  4. Total, Asymmetric-Synthesis of (+)-Castanospermine, (+)-6-Deoxycastanospermine, and (+)-6-Deoxy-6-Fluorocastanospermine
 
research article

Total, Asymmetric-Synthesis of (+)-Castanospermine, (+)-6-Deoxycastanospermine, and (+)-6-Deoxy-6-Fluorocastanospermine

Reymond, J. L.
•
Pinkerton, A. A.
•
Vogel, P.  
1991
The Journal of Organic Chemistry

Bromination of the dibenzyl acetal of (-)-(1S,4S)-7-oxabicyclo[2.2.1]hept-5-en-2-one ((-)-5) led to (+)-(1S,5S,6S,7S)-6-endo-(benzyloxy)-5-exo-bromo-7-oxabicyclo[2.2.1]hept an-2-one (25). Baeyer-Villiger oxidation of 25 gave 2-O-benzyl-3-bromo-3,5-dideoxy-beta-L-arabino-hexofuranosidurono-6,1-lac tone (26). Methanolysis of 26 afforded the corresponding methyl (methyl alpha-beta-L-arabinofuranosid)uronates (27 + 28). The alpha anomer 27 was reduced with DIBAH into methyl 2-O-benzyl-3-bromo-3,5-dideoxy-beta-L-arabino-hexofuranoside (29). Mesylation of the primary alcohol, followed by treatment with NH3 gave methyl 2-O-benzyl-3,5-6-trideoxy-3,6-imino-beta-L-lyxo-hexofuranoside (32). Acetylation of the amine with ClCH2COCl, acetolysis of the methyl furanoside followed by Arbuzov condensation with (EtO)3P, and then intramolecular Horner-Emmons reaction led to (5S,6S,7S)-7-hydroxy-5-(benzyloxy)-1-azabicyclo[4.3.0]non-3-en-2-one (37). Base-catalyzed hydrolysis of the corresponding epoxide 43 ((1S,6S,7S,8R,8aS)-8-(benzyloxy)-6,7-epoxy-1-hydroxyoctahydroindolizidin -5-one) followed by reduction of the lactam and deprotection of the alcoholic functions afforded (+)-castanospermine ((+)-1). The conversion of (-)-5 into (+)-1 was highly stereoselective, requiring the isolation of 10 synthetic intermediates and with an overall yield of 15.2%. Reduction of 43 with BH3.Me2S or its treatment with HF.Et3N allowed one to prepare readily (+)-6-deoxycastanospermine ((+)-2 and 6-deoxy-6-fluorocastanospermine ((+)-3). The crystal structure of (+)-3 is also reported.

  • Details
  • Metrics
Type
research article
DOI
10.1021/jo00006a031
Author(s)
Reymond, J. L.
Pinkerton, A. A.
Vogel, P.  
Date Issued

1991

Published in
The Journal of Organic Chemistry
Volume

56

Issue

6

Start page

2128

End page

2135

Subjects

Pure 7-oxabicyclo<2.2.1>hept-5-en-2-yl derivatives

•

stereoselective

•

total synthesis

•

electron donating substituent

•

alpha-mannosidase

•

inhibitor

•

n-linked oligosaccharides

•

enantiospecific synthesis

•

carbonyl group

•

glucosidase-i

•

naked sugars

•

differential inhibition

Note

Univ lausanne,chim sect,ch-1005 lausanne,switzerland. univ toledo,dept chem,toledo,oh 43606.

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/20.500.14299/219648
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