Synthesis of D- and L-deoxymannojirimycin via an asymmetric aminohydroxylation of vinylfuran.
[figure: see text] The Sharpless catalytic asymmetric aminohydroxylation has been applied to 2-vinylfuran, producing beta-hydroxyfurfurylamine 5a with enantioexcess of > 86% and 21% yield from furfural. The Cbz and TBS protected amino alcohol 5a was converted into both the D- and L-isomers of deoxymannojirimycin (DMJ) and deoxygulonojirimycin in five to seven steps and 48% and 66% overall yields. The key steps include the use of an aza-Achmatowicz reaction, a diastereoselective Luche reduction, diastereoselective dihydroxylation, and a tandem Cbz deprotection/reductive amination.
Haukaas
M H
MH
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
O'Doherty
G A
GA
D017485:1-Deoxynojirimycin / Q000138:chemical synthesis*; D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D005663:Furans / Q000737:chemistry*; D006900:Hydroxylation; D013237:Stereoisomerism
D004791:Enzyme Inhibitors; D005663:Furans; D017485:1-Deoxynojirimycin; C027684:2-vinylfuran