108147-54-2Relevant articles and documents
Transforming flask reaction into cell-based synthesis: Production of polyhydroxylated molecules via engineered Escherichia coli
Wei, Mohui,Li, Zijie,Li, Tiehai,Wu, Baolin,Liu, Yunpeng,Qu, Jingyao,Li, Xu,Li, Lei,Cai, Li,Wang, Peng George
, p. 4060 - 4065 (2015)
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.
A COMBINED CHEMICAL AND ENZYMATIC PROCEDURE FOR THE SYNTHESIS OF 1-DEOXYNOJIRIMYCIN AND 1-DEOXYMANNOJIRIMYCIN
Pederson, Richard L.,Kim, Mahn-Joo,Wong, Chi-Huey
, p. 4645 - 4648 (1988)
1-Deoxynojirimycin and 1-deoxymannojirimycin have been prepared via fructose diphosphate aldolase catalysed condensation followed by catalytic intramolecular reductive amination.
Conformational Behaviour of Azasugars Based on Mannuronic Acid
van Rijssel, Erwin R.,Janssen, Antonius P. A.,Males, Alexandra,Davies, Gideon J.,van der Marel, Gijsbert A.,Overkleeft, Herman S.,Codée, Jeroen D. C.
, p. 1297 - 1304 (2017)
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.
Asymmetric total syntheses of (+)-2,5-dideoxy-2,5-imino-D-glucitol [(+)-DGDP] and (?)-1-deoxymannojirimycin [(?)-DMJ] via an extended chiral 1,3-oxazine
Myeong, In-Soo,Jung, Changyoung,Kim, Ji-Yeon,Park, Seok-Hwi,Ham, Won-Hun
, p. 2422 - 2425 (2018)
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.
PRACTICAL SYNTHESIS OF DEOXYMANNOJIRIMYCIN AND MANNONOLACTAM FROM L-GULONOLACTONE. SYNTHESIS OF L-DEOXYMANNOJIRIMYCIN AND L-MANNONOLACTAM FROM D-GULONOLACTONE.
Fleet, George W. J.,Ramsden, Nigel G.,Witty, David R.
, p. 319 - 326 (1989)
An eight step synthesis of deoxymannojirimycin from L-gulonolactone in 25percent overall yield is reported; the key step is the formation of a δ-lactam by the reduction of a 5-azidolactone.The preparations of mannonolactam from L-gulonolactone and of L-deoxymannojirimycin and L-mannonolactam from D-gulonolactone are described.
A simple access to the D-mannosidase inhibitor, 1-deoxymannojirimycin
Spreitz, Josef,Stuetz, Arnold E.,Wrodnigg, Tanja M.
, p. 183 - 186 (2002)
Crystalline 1,3,4,5-tetra-O-acetyl-6-bromo-6-deoxy-keto-D-fructose was prepared by reaction of 1,3,4,5-tetra-O-acetyl-D-fructopyranose with triphenylphosphane dibromide in dichloromethane. Subsequent deprotection followed by reaction of the free 6-bromodeoxyfructofuranose with sodium azide in N,N-dimethylformamide furnished the corresponding 6-azidodeoxyketose. Catalytic hydrogenation led to 1-deoxymannojirimycin in 27% overall yield from 1,3,4,5-tetra-O-acetyl-D-fructopyranose. This access is simple, inexpensive, high-yielding and clearly suitable for multigram preparations.
Aldolase-Catalyzed C-C Bond Formation for Stereoselective Synthesis of Nitrogen-Containing Carbohydrates
Straub, Alexander,Effenberger, Franz,Fischer, Peter
, p. 3926 - 3932 (1990)
Rabbit muscle aldolase was found to catalyze stereoselective aldol addition of dihydroxyacetone phosphate (1) to 3-azido-2-hydroxypropanal (2).The ketose 1-phosphates were isolated as barium salts, 4a/4b, and hydrolyzed with acid phosphatase.The mixture of 6-azido-6-deoxy-D-fructose (5) and 6-azido-6-deoxy-L-sorbose (6) thus obtained was separated by anion exchange chromatography.Reductive amination of 5 and 6 yielded, respectively, 1-deoxymannojirimycin (7) and 1-deoxynojirimycin (8), with high diastereoselectivity (>98:2).Analogous aldol addition of 1 to 3-azido-2-hydroxybutanal (9) (E:Z=92:8) afforded a mixture of the 6-azido-6,7-dideoxyheptuloses 12 and 13, which contained 88percent of 6-azido-6,7-dideoxy-D-altro-heptulose (13).After anion-exchange chromatography, 13 was isolated as a 18:82 mixture of the α/β anomers.Reductive amination of pure 13 gave a mixture of 2,6,7-trideoxy-2,6-imino-D-glycero-D-manno- and D-gluco-heptitols (14 and 15) (3:2 molar ratio), which likewise was separated by anion-exchange chromatography.If a mixture of 12 and 13 was hydrogenated under identical conditions, 2,6,7-trideoxy-2,6-imino-L-glycero-L-gulo-heptitol (16) could be isolated besides 14 and 15.
Asymmetric synthesis of 1-deoxynojirimycin and its congeners from a common chiral building block
Takahata, Hiroki,Banba, Yasunori,Sasatani, Mayumi,Nemoto, Hideo,Kato, Atsushi,Adachi, Isao
, p. 8199 - 8205 (2004)
A new, promising chiral building block 9 for the synthesis of 1-deoxy-4,5-trans-oriented azasugars such as 1-deoxynojirimycin (1) was prepared in only four steps from the Garner aldehyde 10 using catalytic ring-closing metathesis (RCM) for the construction of the piperidine ring. In practical test, the first synthesis of all four isomers (1 and 6-8) of trans-4,5-orientated 1-deoxyiminosugars using 9 as a common chiral building block was demonstrated. Graphical Abstract
Simple synthetic route to polyhydroxylated pyrrolidines and piperidines
Lee, Sang Gyeong,Park, Ki Hun,Yoon, Yong-Jin
, p. 711 - 715 (1998)
A short and simple synthetic route to polyhydroxylated piperidines and pyrrolidines were described with D-glucurono-δ-lactone as chiral educt. Key reaction steps included selective cleavage of terminal isopropylidene group of compound 12 with Dowex 50W-X8 resin (H+ form), regioselective ring opening of epoxide 16 and intramolecular nucleophilic amination of compound 14 and 18.
A Simple Convergent Synthesis of the Mannosidase Inhibitor 1-Deoxymannonojirimycin from Sucrose
Raadt, Anna de,Stuetz, Arnold E.
, p. 189 - 192 (1992)
The glycosidase inhibitor 1-deoxymannonojirimycin (1,5-dideoxy-1,5-imino-D-mannitol) was synthesized in four simple steps from sucrose via 6,6'-diazido-6,6'-dideoxysucrose and 6-azido-6-deoxy-D-fructofuranose.The "isomeric ballast" of the sequence, 6-azido-6-deoxy-D-glucose, could be partially converted into 6-azido-6-deoxy-d-fructofuranose with the aid of glucose isomerase (E.C. 5.3.1.5) demonstrating a novel synthetic application of this enzyme.The sequence allows access to multigramm quantities of 1-deoxy-mannonojirimycin in over 30percent overall yield without the need for expensive reagents and protecting group manipulations.Key Words: 1-deoxymannonojirimycin, mannosidase inhibitor, glucose isomerase, sucrose, synthesis
