title: Asymmetric syntheses of (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin via a ring-expansion approach.
abstract: The asymmetric syntheses of (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin are described herein. The ring-closing iodoamination of two epimeric bishomoallylic amines to give the corresponding 5-iodomethylpyrrolidines was followed by in situ ring-expansion to give two diastereoisomerically pure (>99:1 dr) cyclic carbonates. Subsequent deprotection gave (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin as single diastereoisomers in 7.4 and 3.3% overall yield, respectively, from commercially available starting materials.
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK. steve.davies@chem.ox.ac.uk
authors.forename: Stephen G
authors.initials: SG
authors.lastname: Davies
authors.forename: Aude L A
authors.initials: AL
authors.lastname: Figuccia
authors.forename: Ai M
authors.initials: AM
authors.lastname: Fletcher
authors.forename: Paul M
authors.initials: PM
authors.lastname: Roberts
authors.forename: James E
authors.initials: JE
authors.lastname: Thomson
mesh_terms: D017485:1-Deoxynojirimycin / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D002254:Carbonates; D002384:Catalysis; D018360:Crystallography, X-Ray; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: C582947:1-deoxyallonojirimycin; D000588:Amines; D002254:Carbonates; D017485:1-Deoxynojirimycin