Synthesis of d- and l-Deoxymannojirimycin via an Asymmetric Aminohydroxylation of Vinylfuran

Abstract

[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.

Five‐Membered Heterocycles: Furan

“…Dimethyldioxirane [139] and methyltrioxorhenium/urea hydrogen peroxide [140] are also effective oxidants. The corresponding aza-Achmatowicz oxidation of furfurylamines [151], frequently by NBS or m-CPBA, provides a novel method for the synthesis of azasugars and piperidine-containing compounds [152]. An interesting example of simultaneously applying both reaction variants in the synthesis of aza-C-linked disaccharide, such as 182 from 181, is shown in Scheme 6.82 [153].…”

syn‐Allylstannation of N‐Acyliminium Intermediates by Tributyl[γ‐(silyloxy)allyl]stannanes: A Key Reaction for the Diastereoselective Synthesis of Polyhydroxypiperidines and Polyhydroxyazepanes

“…A sequence including the hydrogenolysis of the O-benzyl group (H 2 , Pd/C, ethanol, room temp., 24 h) and carbamate deprotection (KOH/ EtOH, heated at reflux) was used to obtain the desired (Ϯ)-1-deoxygulonojirimycine which was finally purified and characterized as its peracetylated derivative 9i. [36] Scheme 4. Reagents and conditions: (a) H 2 , Pd/C (10 mol-%), EtOH, room temp., 24 h; (b) KOH, EtOH, reflux, 24 h; (c) DMAP, 1 mol-%, Ac 2 O, pyridine, room temp., 1 h.…”

Exploitation of Furanoid 5‐Azido‐3‐C‐Branched‐Chain Sugars Towards Highly Functionalized Nitrogen‐Containing Carbohydrate Derivatives

“…[14] 1,2-Dihydropyridin-3-ones are generally obtained in low overall yield by methodologies that usually require several synthetic steps. [15,16] Our approach provided compound 18 after five steps and in 29 % overall yield starting from the readily prepared 5-azido-3-ulose 1. This molecule is structurally suitable to be a useful synthon for new imino sugar derivatives.…”

“…This molecule is structurally suitable to be a useful synthon for new imino sugar derivatives. Enones of this family have been used as key intermediates in the synthesis of natural products, [15,17] including 1-deoxynojirimycin, [17a] deoxymannojirimycin and deoxygulonojirimycin. [15] Conclusions Furanoid (Z)-and (E)-3-C-(ethoxycarbonyl)methylene-5-azido sugars have proved to be useful precursors for the acquisition of carbohydrate or non-carbohydrate molecules comprising an α,β-unsaturated lactone or ketone functionality by reliable approaches involving few synthetic steps.…”