14199-63-4

Upstream product

• 57-04-5 dihydroxyacetone phosphate 
• 114395-07-2 (RS)-3-azido-2-hydroxypropanal 
• 127708-83-2 5-Azido-3,6-di-O-benzyl-5-deoxy-α/β-D-glucofuranose 
• 10030-20-3 1,3-dihydroxyacetone phosphate 
• 94119-04-7 benzyl 5-azido-5-deoxy-α-D-mannofuranoside 
• 94119-08-1 3,4-di-O-benzyl-1,5-dideoxy-1,5-imino-D-mannitol 
• 91364-19-1 5-amino-1-O-benzyl-5-deoxy-2,3-O-isopropylidene-α-D-mannofuranose 
• 176209-15-7 (2R,3S,4R,5R)-1-Tosyl-4,5-diacetoxy-2-hydroxymethyl-3-piperidyl benzoate 
• 121624-22-4 1,5-dideoxy-1,5-imino-4,6-O-isopropylidene-D-mannitol 
• 55221-54-0 1,3,4,5-Tetra-O-acetyl-β-D-fructopyranose 
• 176209-08-8 (2R,6R)-N-Tosyl-6-hydroxy-2-methoxymethyl-1,2,3,6-tetrahydropyridin-3-one 
• 176209-10-2 (2R,3R,6R)-1-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetrahydropyridin-3-ol 
• 176209-09-9 (2R,6R)-N-Tosyl-6-ethoxy-2-methoxymethyl-1,2,3,6-tetrahydropyridin-3-one 
• 176209-12-4 (2R,3S)-1-Tosyl-2-methoxymethyl-1,2,3,6-tetrahydro-3-pyridyl benzoate 

Downstream Products

• 117821-08-6 1,5-dideoxy-1,5-(methyliminiumyl)-D-mannitol 
• 679404-77-4 N-benzyloxycarbonyl-1,5-dideoxy-1,5-imino-D-mannitol 
• 155501-85-2 N-butyl-1-deoxygalactonojirimycin 
• 216758-20-2 (2R,3R,4R,5R)-1-(5-(((3R,5R,7R)-adamantan-1-yl)methoxy)pentyl)-2-(hydroxymethyl)piperidine-3,4,5-triol 
• 223771-83-3 N-nonyl 1-deoxymannojirimycin 
• 679404-78-5 2,6-di-O-pivaloyl-N-benzyloxycarbonyl-1,5-dideoxy-1,5-imino-D-mannitol 

Relevant academic research and scientific papers

Asymmetric total syntheses of (+)-2,5-dideoxy-2,5-imino-D-glucitol [(+)-DGDP] and (?)-1-deoxymannojirimycin [(?)-DMJ] via an extended chiral 1,3-oxazine

The asymmetric total syntheses of (+)-2,5-dideoxy-2,5-imino-D-glucitol [(+)-DGDP] 1 and (?)-1-deoxymannojirimycin [(?)-DMJ] 2 were achieved using an extended chiral 1,3-oxazine. The key synthetic strategies included extension of the chirality of anti,syn-oxazine 3 using diastereoselective dihydroxylation, and piperidine and pyrrolidine ring formation. Starting from readily available anti,syn-oxazine 3, (+)-DGDP 1 was synthesized in 5 steps with 31.6% overall yield and (?)-DMJ 2 was synthesized in 4 steps with 60.6% overall yield.

Conformational Behaviour of Azasugars Based on Mannuronic Acid

A set of mannuronic-acid-based iminosugars, consisting of the C-5-carboxylic acid, methyl ester and amide analogues of 1deoxymannorjirimicin (DMJ), was synthesised and their pH-dependent conformational behaviour was studied. Under acidic conditions the methyl ester and the carboxylic acid adopted an “inverted” 1C4 chair conformation as opposed to the “normal” 4C1 chair at basic pH. This conformational change is explained in terms of the stereoelectronic effects of the ring substituents and it parallels the behaviour of the mannuronic acid ester oxocarbenium ion. Because of this solution-phase behaviour, the mannuronic acid ester azasugar was examined as an inhibitor for a Caulobacter GH47 mannosidase that hydrolyses its substrates by way of a reaction itinerary that proceeds through a 3H4 transition state. No binding was observed for the mannuronic acid ester azasugar, but sub-atomic resolution data were obtained for the DMJ?CkGH47 complex, showing two conformations—3S1 and 1C4—for the DMJ inhibitor.

Transforming flask reaction into cell-based synthesis: Production of polyhydroxylated molecules via engineered Escherichia coli

Dihydroxyacetone phosphate (DHAP)-dependent aldolases have been intensively studied and widely used in the synthesis of carbohydrates and complex polyhydroxylated molecules. However, strict specificity toward donor substrate DHAP greatly hampers their synthetic utility. Here, we transformed DHAP-dependent aldolases-mediated by in vitro reactions into bioengineered Escherichia coli (E. coli). Such flask-to-cell transformation addressed several key issues plaguing in vitro enzymatic synthesis: (1) it solves the problem of DHAP availability by in vivo-hijacking DHAP from the glycolysis pathway of the bacterial system, (2) it circumvents purification of recombinant aldolases and phosphatase, and (3) it dephosphorylates the resultant aldol adducts in vivo, thus eliminating the additional step for phosphate removal and achieving in vivo phosphate recycling. The engineered E. coli strains tolerate a wide variety of aldehydes as acceptor and provide a set of biologically relevant polyhydroxylated molecules in gram scale.

Asymmetric syntheses of (-)-1-deoxymannojirimycin and (+)-1- deoxyallonojirimycin via a ring-expansion approach

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.

Asymmetric synthesis of 1-deoxyazasugars from chiral aziridines

A general and facile synthesis of enantiopure 1-deoxyazasugars was achieved from stereoselective dihydroxylation of a common synthetic intermediate, piperidine ring fused oxazolidin-2-one, originating from a commercially available starting substrate, chiral aziridine-2-carboxylate, in high yields. The Royal Society of Chemistry 2011.

Straightforward synthesis of diverse 1-deoxyazapyranosides via stereocontrolled nucleophilic additions to six-membered cyclic nitrones

A systematic study of diastereoselective nucleophilic addition of Grignard reagents to six-membered chiral tri-O-benzyl cyclic nitrones is described. With all eight chiral cyclic nitrones and asymmetric reaction conditions in hand, a practical methodology is established for the preparation of diverse 1-deoxyazapyranosides bearing various stereogenic centers. We have developed practical methods to prepare all eight six-membered chiral cyclic nitrones. Using these cyclic nitrones and diastereoselective nucleophilic additions, 12 examples of diverse 1-deoxyazapyranosides including enantiomers were synthesized to demonstrate the generality and flexibility of this new approach.

An expeditious synthesis of iminosugars

A short and expedient synthesis of the potent glycosidase inhibitors, 1-deoxynojirimycin, miglitol, miglustat, 1-deoxymannojirimycin, and 1-deoxygalactonojirimycin is presented.

D-fructose-6-phosphate aldolase in organic synthesis: Cascade chemical-enzymatic preparation of sugar-relafed polyhydroxylated compounds

Novel aldol addition reactions of dihydroxyacetone (DHA) and hydroxyacetone (HA) to a variety of aldehydes catalyzed by D-fructose-6-phosphate aldolase (FSA) are presented. In a chemical-enzymatic cascade reaction approach, 1-deoxynojirimycin and 1-deoxymannojirimycin were synthesized starting from (R)- and (S)-3-(N-Cbz-amino)-2-hydroxypropanal, respectively. Furthermore, 1,4-dideoxy1,4-imino-D-arabinitol and 1,4,5-trideoxy-1,4-imino-D-arabinitol were prepared from N-Cbz-glycinal, 1 -Deoxy-D-xylulose was also synthesized by using HA as the donor and either 2-benzyloxyethanal or 2-hydroxyethanal as acceptors. In both cases the enzymatic aldol addition reaction was fully stereoselective, but with 2-hydroxyethanal 17% of the epimeric product at C2, 1-deoxy-D-erythro-2-pentulose, was observed due to enolization/epimerization during the isolation steps. It was also observed that D-(-)-threose is a good acceptor substrate for FSA, opening new synthetic possibilities for the preparation of important novel complex carbohydrate-related compounds from aldoses. To illustrate this, 1-deoxy-D-ido-hept-2-ulose was obtained stereoselectively by the addition of HA to D-(-)-threose, catalyzed by FSA. It was found that the reaction performance depended strongly on the donor substrate, HA being the one that gave the best conversions to the aldol adduct. The examples presented in this work show the valuable synthetic potential of FSA for the construction of chiral complex polyhydroxylated sugar-type structures.

Regioselective intramolecular ring closure of 2-amino-6-bromo-2,6- dideoxyhexono-1,4-lactones to 5- or 6-membered iminuronic acid analogues: Synthesis of 1-deoxymannojirimycin and 2,5-dideoxy-2,5-imino-d-glucitol

1-Deoxymannojirimycin (8c) was synthesised from 2-amino-6-bromo-2,6- dideoxy-d-mannono-1,4-lactone (7) by intramolecular direct displacement of the C-6 bromine employing non-aqueous base treatment followed by reduction of the intermediate methyl ester. Li