15218-38-9Relevant articles and documents
Imino and amino sugar purification
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Page/Page column 5, (2008/06/13)
Novel processes for the purification of an imino or amino sugar, such as D-1-deoxygalactonojirimycin (DGJ). Particularly, there are described processes for the purification of multi-kilogram scale sugars using hydrochloric acid.
Stereoselective Homologation-Amination of Aldehydes by Addition of Their Nitrones to C-2 Metalated Thiazoles - A General Entry to α-Amino Aldehydes and Amino Sugars
Dondoni, Alessandro,Franco, Santiago,Junquera, Federico,Merchan, Francisco L.,Merino, Pedro,et al.
, p. 505 - 520 (2007/10/03)
A general method for the homologation of aldehydes to α-amino aldehydes (aminohomologation) has been developed, which employs nitrones as iminium derivatives of the aldehydes.Key operations include a) the addition of a thiazole metalated at C-2 to the N-benzylnitrone derived from the aldehyde, b) the reductive dehydroxylation of the resultant thiazolyl N-benzylhydroxylamine, and c) the unmasking of the formyl group from the thiazole ring.The homologation sequence was studied by employing nitrones derived from various chiral polyalkoxy aldehydes and dialdoses.The addition of 2-lithiothiazole to these nitrones was syn-selective, whereas the reaction with the same nitrones precomplexed with Lewis acids was anti-selective.Hence, from each nitrone a pair of diastereoisomeric hydroxylamines was obtained.These compounds were then converted by the above sequence into α-epimeric α-amino aldehydes.Model elaborations of some of these products afforded the amino sugars D-glucosamine, D-mannosamine, D-nojirimycin, and advanced intermediates for the synthesis of destomic acid and lincosamine. - Keywords: amino aldehydes; aminohomologation; amino sugars; nitrones; thiazoles
Amidine, amidrazone, and amidoxime derivatives of monosaccharide aldonolactams: Synthesis and evaluation as glycosidase inhibitors
Papandreou,Tong,Ganem
, p. 11682 - 11690 (2007/10/02)
The synthesis of amidine, amidrazone, and amidoxime derivatives of D-glucono, D-mannono, and D-galactonolactams, which are potent glycosidase inhibitors, is described. With their sugar-like structures and resonance-stabilized, partially positively charged anomeric carbons, these monosaccharide analogs mimic key conformational and electrostatic features of the corresponding glycopyranosyl cations. In the D-gluco series, all three derivatives are potent inhibitors of sweet almond β-glucosidase. Levels of inhibition remain nearly constant despite a 105 change in basicity, indicating that conformational flattening of the hydrolysis intermediate is more important for transition-state binding by the enzyme than charge development. The same D-gluco derivatives also interact with mannose- and galactose-processing enzymes. Considerably weaker inhibition is observed with 1β-amino-1-deoxynojirimycin, which embodies similar endocyclic and exocyclic nitrogens in an undistorted chair conformation. In the D-manno series, the amidrazone and amidoxime are potent inhibitors of jackbean α-mannosidase, mung bean α-mannosidase, fungal β-mannosidase, Golgi α-mannosidase I, α-mannosidase II, and soluble (or endoplasmic reticulum) α-mannosidase. The mannoamidrazone also inhibits Golgi α-mannosidase I and the endoplasmic reticulum mannosidase in vivo. In the D-galacto series, significant inhibition of almond β-glucosidase, bovine liver β-galactosidase, and green coffee bean α-galactosidase is observed, but little or no inhibition of amyloglucosidase.
Synthesis of (+)- and (-)-nojirimycin and their 1-deoxy derivatives from myo-inositol
Chida,Furuno,Ikemoto,Ogawa
, p. 185 - 194 (2007/10/02)
The conversion of the naturally abundant cyclitol, myo-inositol (4), into (+)-nojirimycin (1a), its enantiomer (1b), and their 1-deoxy analogues (2a and 2b) is described. Biological assay of 2a, 2b, and the bisulfite adducts of 1a and 1b (3a and 3b) showed that the compounds having the unnatural L-gluco configuration (2b and 3b) possess moderate-to-high inhibitory activity against almond β-D-glucosidase and bovine liver β-D-galactosidase.
Stereocontrolled Total Synthesis of Galactostasin from Serine
Dondoni, Alessandro,Merino, Pedro,Perrone, Daniela
, p. 1576 - 1578 (2007/10/02)
An efficient stereoselective total synthesis of (-)-galactostasin (-)-1 from N-tert-butoxycarbonyl-2,3-isopropylidene L-serine methyl ester (21percent overall yield) is described via thiazole intermediates serving as protected aldehydes; the parallel synt
A FACILE SYNTHESIS OF NOJIRIMYCIN
Rajanikanth, B.,Seshadri, R.
, p. 755 - 758 (2007/10/02)
Expetitious new synthesis of the title compound 5 in high yield from δ-gluconolactone 2 via intermediate 4 and 5 has been described.
PRACTICAL SYNTHESIS OF NOJIRIMYCIN
Tsuda, Yoshisuke,Okuno, Yukihiro,Kanemitsu, Kimihiro
, p. 63 - 66 (2007/10/02)
The short step and efficient synthesis of nojirimycin (1) from commercially available 1,2-isopropylidene-D-glucofuranose (2) was described.Oxidation of 2 with (Bu3Sn)2O-Br2 followed by oximation, isomerization, and stereoselective reduction gave the 5-amino derivative of gluco-configuration (6a), which was converted to nojirimycin bisulfite adduct (8) in 50percent overall isolated yield.
Total Synthesis of (+)-Nojirimycin and (+)-1-Deoxynojirimycin
Iida, Hideo,Yamazaki, Naoki,Kibayashi, Chihiro
, p. 3337 - 3342 (2007/10/02)
An efficient chiral synthesis of (+)-nojirimycin (1) and (+)-1-deoxynojirimycin (2) has been achieved in optically pure form via the common intermediate 11 derived from the nonsugar chiral pool.The monosilyl derivative 4 of 2,3-O-isopropylidene-L-threitol (3) was converted to the (E)-allyl alcohol 8, which upon asymmetric epoxidation provided the syn epoxide 9.Regio- and stereoselective epoxide opening reaction of 9 followed by methoxymethylation yielded the azide 11, which afforded in five steps (+)-1-deoxynojirimycin (2).The azide 11 could also serve as the intermediate for the synthesis of (+)-nojirimycin (1), which was thus derived from 11 in six steps.
Synthesis of 5-amino-5-deoxy-D-galactopyranose and 1,5-dideoxy-1,5-imino-D-galactitol, and their inhibition of alpha- and beta-D-galactosidases.
Legler,Pohl
, p. 119 - 129 (2007/10/02)
A 12-step route is presented starting from 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose for the preparation of the title compounds and their L-altro analogues. Their synthesis is based on the reduction with Raney nickel of a protected 5-hydroxyimino derivative of L-arabino-hexofuranos-5-ulose, with the following improvements for the preparation of a D-galactofuranose derivative: oxidation at C-3 with pyridinium dichromate-acetic anhydride, stereospecific reduction of a 3-O-acetyl-hex-3-enofuranose intermediate to the D-gulo derivative, and inversion at C-3 of its 3-tosylate with tetrabutylammonium acetate in chlorobenzene. alpha-D-Galactosidase from coffee beans and from Escherichia coli and beta-D-galactosidase from E. coli and Aspergillus wentii were inhibited with Ki values that ranged from 0.0007 to 8.2 microM. Formation of the enzyme-inhibitor complexes with the D-galactose analogue was on the time-scale of minutes, whereas the D-galactitol analogue showed a slow approach to the inhibition only with alpha-D-galactosidase from coffee beans and beta-D-galactosidase from A. wentii. N-Alkylation of the D-galactitol analogue was detrimental to the inhibition except for beta-D-galactosidase from E. coli and beta-D-glucosidase from almonds, but, even with these enzymes, the observed affinity enhancements were 10(2) to 10(3)-times smaller than those of N-alkylated D-galactosylamine and D-glucosylamine.
