26301-79-1Relevant articles and documents
Improved synthesis of 6-amino-6-deoxy-D-galactono-1,6-lactam and D-mannono-1,6-lactam from corresponding unprotected D-hexono-1,4-lactones
Chaveriat, Ludovic,Stasik, Imane,Demailly, Gilles,Beaupère, Daniel
, p. 2079 - 2081 (2004)
Regioselective bromination of unprotected D-galactono-1,4-lactone and D-mannono-1,4-lactone with PPh3/CBr4 led to 6-bromo-6-deoxy derivatives. These intermediates were treated with LiN 3 and hydrogenated to give 6-amino-6-deoxy-D-galactono-1,6-lactam (8) and 6-amino-6-deoxy-D-mannono-1,6-lactam (13) in 74 and 67% overall yield, respectively.
Facile syntheses of 1-deoxynojirimycin (DNJ) and 1-deoxymannojirimycin (DMJ)
Song, Xuezheng,Hollingsworth, Rawle I.
, p. 3115 - 3118 (2007)
1-Deoxynojirimycin (DNJ) and 1-deoxymannojirimycin (DMJ) were synthesized through a concise and practicable pathway. A strategy of using carbohydrate derivatives bearing two leaving groups in the preparation of azasugars by di-N-alkylation of amines was developed. The strategy involved the selective partial protection of dibromo alditols.
δ-Galactonolactone: Synthesis, isolation, and comparative structure and stability analysis of an elusive sugar derivative
Bierenstiel, Matthias,Schlaf, Marcel
, p. 1474 - 1481 (2007/10/03)
δ-D-Gluconolactone, δ-D-mannonolactone, and - for the first time - the thermodynamically unstable δ-D-galactonolactone have been prepared and isolated from DMF solution by oxidizing the corresponding sugars with Shvo's catalyst [(C4Ph4CO)(CO)2Ru] 2 and a hydrogen acceptor. The preferred conformation of δ-D-galactonolactone in [D6] DMSO solution has been determined by 1H NMR spectroscopy experiments and DFT calculations to be 4H3 and is compared to those of the previously established conformations of δ-D-gluconolactone (4H3) and δ-D-mannonolactone (B2,5), The conformations of the lactones suggest an explanation for their relative rates of isomerization to their respective γ-D-lactones by an intramolecular mechanism. Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Germany, 2004.
Syntheses of (3R,4R,5R,6R)-tetrahydroxyazepane (1,6-dideoxy-1,6-imino-D-mannitol) and (3S,4R,5R,6R)-tetrahydroxyazepane (1,6-dideoxy-1,6-imino-D-glucitol)
Joseph, Cosam C,Regeling, Henk,Zwanenburg, Binne,Chittenden, Gordon J.F
, p. 6907 - 6911 (2007/10/03)
Syntheses of 1,6-dideoxy-1,6-imino-D-mannitol (D-mannoazepane) (1) and 1,6-dideoxy-1,6-imino-D-glucitol (D-glucoazepane) (3) from D-isoascorbic acid and D-glucono-1,5-lactone, respectively, are described. The key step in both routes involved reductive aminative 1,6-cyclization with retention of configurations to give the corresponding lactams, which were subsequently reduced to afford compounds 1 and 3 in 24 and 28.5%, overall yield, respectively.
Kinetics and mechanism of the reduction of chromium(VI) and chromium(V) by D-glucitol and D-mannitol
Roldan, Viviana P.,Daier, Veronica A.,Goodman, Bernard,Santoro, Mabel I.,Gonzalez, Juan Carlos,Calisto, Nancy,Signorella, Sandra R.,Sala, Luis F.
, p. 3211 - 3228 (2007/10/03)
The oxidation of D-glucitol and D-mannitol by CrVI yields the aldonic acid (and/or the aldonolactone) and CrIII as final products when an excess of alditol over CrVI is used. The redox reaction occurs through a CrVI → CrV → CrIII path, the CrVI → CrV reduction being the slow redox step. The complete rate laws for the redox reactions are expressed by: a) - d[CrVI]/dt = {kM2H [H-]2 +kMH [H+]}[mannitol][CrVI], where kM2H = (6.7 ± 0.3) · 10-2 M-3 S-1 and kMH = (9±2) · 10-3 M-2 S-1: b) - d [CrVI] /dt = {kG2H[H+]2 + kGH [H+]}[GLUCITOL][CrVI]. where kG2H = (8.5 ± 0.2) · 10-2 M-3 S-1 and kGH = (1.8 ± 0.1) · 10-2 M-2S-1 at 330. The slow redox steps are preceded by the formation of a CrVI oxy ester with λMAX 371 nm. at pH 4.5. In acid medium, intermediate CrV reacts with the substrate faster than CrVI does. The EPR spectra show that five- and six-coordinate oxo-CrV intermediates are formed, with the alditol or the aldonic acid acting as bidentate ligands. Pentacoordinate oxo-CrV species are present at any [H+], whereas hexacoordinate ones are observed only at pH V species are not observed, CrV complexes are stable enough to remain in solution for several days to months.
A new efficient access to glycono-1,4-lactones by oxidation of unprotected itols by catalytic hydrogen transfer with RhH(PPh3)4-benzalacetone system
Isaac,Aizel,Stasik,Wadouachi,Beaupère
, p. 475 - 476 (2007/10/03)
Treatment of unprotected pentitols and hexitols with RhH(PPh3)4-benzalacetone system leads exclusively to glycono-1,4-lactones in 60-96% yield.
A NEW AND DIRECT ACCESS TO GLYCONO-1,4-LACTONES FROM GLYCOPYRANOSES BY REGIOSELECTIVE OXIDATION AND SUBSEQUENT RING RESTRICTION
Isaac, Isabelle,Stasik, Imane,Beaupere, Daniel,Uzan, Raoul
, p. 383 - 386 (2007/10/02)
Treatment of partially protected or unprotected carbohydrates with the RhH(PPh3)4-benzalacetone system leads exclusively to glycono-1,4-lactones by regioselective oxidation and subsequent ring restriction.
2-Acetamido-2-deoxyaldonolactones from sugar formazans
Zsoldos-Mady, Virag,Pinter, Istvan,Neszmelyi, Andras,Messmer, Andras,Perczel, Andras
, p. 85 - 96 (2007/10/02)
A new approach towards simple aldonic acid derivatives starting from the corresponding aldoses via the 2-acetamido-2-deoxy formazans resulted in the synthesis of 2-acetamido-2-deoxy-D-galactono-1,4-lactone (8), and its 6-deoxy (11) and 6-azido-6-deoxy (14) analogues on treatment with trifluoroacetic acid.The five-membered ring structure of the lactones and that of the intermediate lactone phenylhydrazone (7) was proved by 1H and 13C NMR studies, including deuterium-induced differential isotope shift (DIS) measurements.With sodium borohydride, lactones 8 and 11 were converted into 2-acetamido-2-deoxy-D-galactitol (15) and its 6-deoxy analogue (17), respectively.
Microbial Oxidation of Aromatics in Enantiocontrolled Synthesis. Part 1.Expedient and General Asymmetric Synthesis of Inositols and Carbohydrates via and Unusual Oxidation of a Polarized Diene with Potassium Permanganate
Hudlicky, Tomas,Mandel, Martin,Rouden, Jacques,Lee, Robert S.,Bachmann, Bryan,et al.
, p. 1553 - 1568 (2007/10/02)
This paper reports on the details of a general design of carbohydrates and cyclitols from biocatalytically derived synthons.Homochiral 1-halogenocyclohexa-4,6-diene-2,3-diols 1a and 1b have been generated from chloro- and bromobenzene, respectively, by means of bacterial dioxygenase of Pseudomonas putida 39D.These chiral synthons have been manipulated to cyclitols and carbohydrates by further stereoselective functionalizations.The preperation of D-chiro-inositol, neo-inositol, muco-inositol, and allo-inositol exemplifies their use in enantiocontrolled synthesis.A novel oxidation of polarized dienes with KMnO4 resulted in the synthesis of α-halogeno epoxy diols, which proved unexpectedly stable.A mechanism is proposed for this transformation and placed in context with the only four reported examples of this reaction in the literature.In addition to the application of this new chemistry to the synthesis of cyclitols, chloro epoxy diol 21a has been transformed into a series of cyclitol synthons by reductive or hydrolytic operations.Reaction of 21a with ammonia led to the preparation of highly oxygenated pyrazines, whose structure were proven by X-ray crystallography.The use of 21a in the preparation of D-chiro-3-inosose, a hitherto unreported cyclitol derivative, is also reported.In addition, chloro epoxy diol 21a was transformed into D-erythruronolactone, completing the synthesis of this important chiral pool reagent in two operations from chlorobenzene.Oxidative cleavage of tetrol 20 yielded D-mannosolactone identical with an authentic sample.
Metal-mediated decarbonylation and dehydration of ketose sugars
Andrews, Mark A.
, p. 2703 - 2708 (2008/10/08)
Ketose sugars can be decarbonylated and/or dehydrated by the action of certain metal complexes. Fructose reacts with 1 equiv of RhCl(PPh3)3 (1) in N-methyl-2-pyrrolidinone (NMP) at 130°C to give furfuryl alcohol, Rh(CO)Cl(PPh3)2 (2), and a small amount of 1-deoxyerythritol. 1,3-Dihydroxyacetone consumes 2 equiv of 1, giving methane and ca. 2 mol of 2. With manno-2-heptulose the primary product is 2,7-anhydromanno-2-heptulopyranose. The mechanisms of these unusual reactions have been studied by using 13C-labeling experiments and model reactions employing Pd(II) and HCl. Attempts to make the reactions catalytic using [Rh(Ph2PCH2CH2CH2PPh 2)2]+[BF4]- in place of 1 were not successful. The use of NMP as a solvent offers some advantages in the acid-catalyzed synthesis of certain carbohydrate dehydration products, as exemplified by the conversion of manno-2-heptulose to its 2,7-anhydride and of 2-deoxyglucose to 1-(2-furanyl)-1,2-ethanediol.
