Iminosugars via Ring-Expansion Processes

The ring-closing iodoamination of enantiopure bishomoallylic amines gives the corresponding C(5)-iodomethyl substituted pyrrolidines. This is followed by in situ ring-expansion to give diastereoisomerically pure (>99:1 dr) cyclic carbonates via ring-opening of the corresponding aziridinium ions with a tethered nucleophile. Subsequent deprotection gave (–)-1-deoxymannojirimycin as a single diastereoisomer. This methodology has also been adapted for the synthesis of the corresponding deoxyamino analogues by trapping of isocyanate reagents to effect intramolecular ring-opening of the key aziridinium intermediates.
 

Key Recent Publications: 

  1. Asymmetric syntheses of (–)-ADMJ and (+)-ADANJ: 2-deoxy-2-amino analogues of
    (–)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin
    Davies, S. G.; Figuccia A. L. A.; Fletcher, A. M.; Roberts, P. M.; Thomson, J. E. J. Org. Chem. 201681, 6481 [View Journal Page]
  2. Asymmetric syntheses of 2,5-dideoxy-2,5-imino-D-glucitol [(+)-DGDP] and 1,2,5-trideoxy-1-amino-
    2,5-imino-D-glucitol [(+)-ADGDP]
    Davies, S. G.; Figuccia, A. L. A.; Fletcher, A. M.; Roberts, P. M.; Thomson, J. E. Tetrahedron 201470, 3601 [View Journal Page]
  3. Asymmetric syntheses of (–)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin via a ring-expansion approach
    Davies, S. G.; Figuccia, A. L. A.; Fletcher A. M.; Roberts, P. M.; Thomson, J. E. Org. Lett. 201315, 2042
    [View Journal Page]

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