Synthesis of D- and L-deoxymannojirimycin via an asymmetric aminohydroxylation of vinylfuran

[GRAPHICS] 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.