63734-12-3

Upstream product

• 18162-48-6 tert-butyldimethylsilyl chloride 
• 97-30-3 methyl-alpha-D-glucopyranoside 
• 82112-21-8 N,O-bis(tertbutyldimethylsilyl)acetamide 
• 29681-57-0 tert-butyldimethylsilane 
• 1824-94-8 methyl beta-D-galactopyranoside 
• 143422-89-3 (2-methylallyl)tertiobutyl-dimethylsilane 

Downstream Products

• 128142-70-1 methyl 2,3,4-tri-O-benzoyl-6-O-(tert-butyldimethylsilyl)-α-D-glucopyranoside 
• 97-30-3 methyl-alpha-D-glucopyranoside 
• 63734-11-2 acetic acid 3,5-diacetoxy-2-(tert-butyldimethylsilanyloxymethyl)-6-methoxytetrahydropyran-4-yl ester 
• 34234-44-1 methyl 2,3,4-tri-O-benzoylglucopyranoside 
• 151725-51-8 methyl 6-O-(2-O-benzoyl-3-O-para-methoxybenzyl-β-D-glucopyranosyl)-2,3,4-tri-O-benzoyl-α-D-glucopyranoside 
• 1340482-37-2 methyl 2-O-(2',3',4',6'-tetra-O-benzyl-α-D-glucopyranosyl)-α-D-glucopyranoside 
• 1340482-38-3 methyl 2-O-(2',3',4',6'-tetra-O-benzyl-β-D-glucopyranosyl)-α-D-glucopyranoside 
• 1340482-39-4 methyl 3-O-(2',3',4',6'-tetra-O-benzyl-α-D-glucopyranosyl)-α-D-glucopyranoside 
• 1340482-40-7 methyl 3-O-(2',3',4',6'-tetra-O-benzyl-β-D-glucopyranosyl)-α-D-glucopyranoside 
• 1379595-09-1 methyl 2,3,4-tri-O-[6-(4-cyanobiphenyl-4'-yloxy)hexanoyl]-α-D-glucopyranoside 
• 1379595-11-5 1-O-methyl 2,3,4-tri-O-[6-(4-cyanobiphenyl-4'-yloxy)hexanoyl]-α-D-glucopyranuronic acid 
• 1379595-07-9 methyl 2,3,4-tri-O-[6-(4-cyanobiphenyl-4'-yloxy)hexanoyl]-6-O-tert-butyldimethylsilyl-α-D-glucopyranoside 
• 1366422-96-9 tert-butyl N-allyl-((2S,3S,4R)-2,3,4-tris(benzyloxy)hex-5-en-1-yl)carbamate 
• 1366422-98-1 (5R,6S,7S)-tert-butyl 5,6,7-tris(benzyloxy)-5,6,7,8-tetrahydroazocine-1(2H)-carboxylate 

Relevant academic research and scientific papers

DABCO: An efficient promoter for the acetylation of carbohydrates and other substances under solvent-free conditions

A simple, mild and efficient solvent-free method for the acetylation of carbohydrates, and their partially protected derivatives, as well as non-carbohydrate substances in excellent yields in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) is described with the advantage of tolerance to various functional groups, short reaction time and ease of product isolation.

32. Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphin/Azodicarbonsaure-diathylester

Reaction of methyl 2,6-bis-O-(t-butyldimethylsilyl)-β-D-glucopyranoside (1a) with triphenylphosphine (TPP)/diethyl azodicarboxylate (DEAD) and Ph3P.HBr or methyl iodide yields methyl 3-bromo-2,6-bis-O-(t-butyldimethylsilyl)-3-deoxy-β-D-allopyranoside (3a) and the corresponding 3-deoxy-3-iodo-alloside 3c (Scheme 1).By a similar way methyl 2,6-bis-O-(t-butyldimethylsilyl)-α-D-glucopiranoside (2a) can be converted to the 4-bromo-4-deoxy-galactoside 4a and the 4-deoxy-4-iodo-galactoside 4b.In the absence of an external nucleophile the sugar derivatives 1a and 2a react with TPP/DEAD to form the 3,4-anhydro-α- or -β-D-galactosides 5 and 6a, respectively, while methyl 4,6-bis-O-(t-butyldimethylsilyl)-β-D-glucopyranoside (1b) yields methyl 2,3-anhydro-4,6-bis-O-(t-butyldimethylsilyl)-β-D-allopyranoside (7a, s.Scheme 2).Even the monosilylated sugar methyl 6-O-(t-butyldimethylsilyl)-α-D-gluco yranoside can be transformed to methyl 2,3-anhydro-6-O-(t-butyldimethylsilyl)-α-D-allopyranoside (8; 56percent) and 3,4-anhydro-α-D-galactopyranoside 6 (10percent), whereas methyl 6-O-(tbutyldimethylsilyl)-β-D-glucopyranoside (1c) yields the 2,3-anhydro-β-D-alloside 7 (46percent) and the 3,4-anhydro-β-D-alloside 9 (23percent, s.Scheme 3).Reaction of 1c with TPP/DEAD/HN3 leads to methyl 3-azido-6-O-(t-butyldimethylsilyl)-3-deoxy-β-D-allopyranoside (10).The epoxides 7 and 8 were converted with NaNH3/NH4Cl to the 2-azido-2-deoxy-altrosides 11 and 13, respectively, and the 3-azido-3-deoxy-glucosides 12 and 14, respectively (Scheme 4 and 5).Reaction of 7 and 8 with TPP/DEAD/HN3 or p-nitrobenzoic acid afforded methyl 2,3-anhydro-4-azido-6-O-(t-butyldimethylsilyl)-4-deoxy-α- and -β-D-gulopyranoside (15 and 17), respectively, or methyl 2,3-anhydro-6-O-(t-butyldimethylsilyl)-4-O-(p-nitrobenzoyl)-α- and -β-D-gulopyranoside (16 and 18), respectively, without any opening of the oxirane ring (s.Scheme 6). - The 2-acetamido-2-deoxy-glucosides 19a and 20a react with TPP/DEAD alone to form the corresponding methyl 2-acetamido-3,4-anhydro-6-O-(t-butyldimethylsilyl)-2-deoxy-galactopyranosides (21 and 22) in a yield of 80 and 85percent, respectively (Scheme 7).With TPP/DEAD/HN3 20a is transformed to methyl 2-acetamido-3-azido-6-O-(t-butyldimethylsilyl)-2,3-didesoxy-β-D-allopyranoside (25, Scheme 8).By this way methyl 2-acetamido-4-azido-3,6-bis-O-(t-butyldimethylsilyl)-2,4-dideoxy-α-D-galactopyranoside (23; 16percent) and the isomerized product methyl 2-acetamido-4,6-bis-O-(t-butyldimethylsilyl)-2-deoxy-α-D-glucopyranoside (19d; 45percent).Under the same conditions the disilylated methyl 2-acetamido-2-deoxy-glucoside 20b leads to methyl 2-acetamido-4-azido-3,6-bis-O-(t-butyldimethylsilyl)-2,4-dideoxy-β-D-galactopyranoside (24). - All structures were assigned by 1H-NMR. analysis of the corresponding acetates.

Effect of solvation on the rotation of hydroxymethyl groups in carbohydrates

The solvent dependences of the populations of the hydroxymethyl rotamers of methyl 2,3,4,6-tetra-O-[2H3]-α-D-glucopyranoside (2a) and methyl 2,3,4- tri-O-[2H3]-α-D-glucopyranoside (6) in 10 and 8 solvents, respectively, have been determined by analysis of 3J(H5,H6R) and 3J(H5,H6S) values and by consideration of evidence for hydrogen bonding through infrared spectroscopy and 3J(H,OH) values. The methods used to determine coupling constants in individual hydroxymethyl rotamers were reexamined, and an improved protocol was developed. When 0-6 is methylated (2a), the populations of the hydroxymethyl rotamers are largely independent of solvent polarity at ratios of about 61:38:0 gg:gt:tg, except that a small population (4%) of the tg rotamer appears in the most polar solvents at the expense of the gg rotamer. When 0-6 is unsubstituted (6), there are substantial changes in rotamer population as solvent polarity increases due to loss of intramolecular hydrogen bonding and stabilization of the more polar rotamers. The rotamer populations for 6 return to those adopted by the permethylated derivative (2a) in the most polar solvents. It was concluded that hydrogen bond donation from OH-6 to water is not important in determining hydroxymethyl rotational preferences. The well-known 'reversed' chemical shift order of the two C6 protons of peracetylated glucopyranose derivatives was shown to also occur for permethylated derivatives and is ascribed to solvent effects in addition to anisotropy. The solvent effect on the chemical shift difference is attributed to the fact that one of the two protons stays on the same side of the pyranose ring in the two more populated rotamers while the other proton exchanges environments.

Discriminating non-ylidic carbon-sulfur bond cleavages of sulfonium ylides for alkylation and arylation reactions

A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described. The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond. Under acidic conditions, sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations. While under alkaline conditions, cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently. The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.

Catalytic Site-Selective Carbamoylation of Pyranosides

Carbamate-bearing carbohydrates contribute to the pharmacological properties of various natural glycosides. The catalytic site-selective carbamoylation of minimally protected pyranosides was achieved for the first time to bypass protection/deprotection sequences. 1-Carbamoylimidazoles were used as the carbamoylation reagents to circumvent the harmful and unstable phosgene and isocyanates. This borinic acid catalyzed transformation granted an expedient access to the tumor cell-binding carbamoylmannoside moiety of bleomycins and analogs in yields of 56% to 89%.

Synthesis and biological evaluation of 1,6-bis-triazole-2,3,4-tri-O-benzyl-α-D-glucopyranosides as a novel α-glucosidase inhibitor in the treatment of Type 2 diabetes

A novel series of 1,6-bis-triazole-benzyl-α-glucoside derivatives (7a-7ee) were designed, synthesized and evaluated for inhibitory activity against α-glucosidase. Most of the synthesized compounds exhibited good activity with IC50 ranging from

Addressing the biochemical foundations of a glucose-based "trojan horse"-strategy to boron neutron capture therapy: From chemical synthesis to in vitro assessment

Boron neutron capture therapy (BNCT) for cancer is on the rise worldwide due to recent developments of in-hospital neutron accelerators which are expected to revolutionize patient treatments. There is an urgent need for improved boron delivery agents, and herein we have focused on studying the biochemical foundations upon which a successful GLUT1-targeting strategy to BNCT could be based. By combining synthesis and molecular modeling with affinity and cytotoxicity studies, we unravel the mechanisms behind the considerable potential of appropriately designed glucoconjugates as boron delivery agents for BNCT. In addition to addressing the biochemical premises of the approach in detail, we report on a hit glucoconjugate which displays good cytocompatibility, aqueous solubility, high transporter affinity, and, crucially, an exceptional boron delivery capacity in the in vitro assessment thereby pointing toward the significant potential embedded in this approach.

Using DMF as Both a Catalyst and Cosolvent for the Regioselective Silylation of Polyols and Diols

Highly regioselective silylation of primary hydroxyl groups of unprotected polyols and diols was obtained by the use of a mixed solvent of MeCN/DMF (10:1) in this study. DMF was discovered to be a good catalyst in this reaction, although the silylation us

Structure–Activity Studies of N-Butyl-1-deoxynojirimycin (NB-DNJ) Analogues: Discovery of Potent and Selective Aminocyclopentitol Inhibitors of GBA1 and GBA2

Analogues of N-butyl-1-deoxynojirimycin (NB-DNJ) were prepared and assayed for inhibition of ceramide-specific glucosyltransferase (CGT), non-lysosomal β-glucosidase 2 (GBA2) and the lysosomal β-glucosidase 1 (GBA1). Compounds 5 a–6 f, which carry sterically demanding nitrogen substituents, and compound 13, devoid of the C3 and C5 hydroxy groups present in DNJ/NB-DGJ (N-butyldeoxygalactojirimycin) showed no inhibitory activity for CGT or GBA2. Inversion of stereochemistry at C4 of N-(n-butyl)- and N-(n-nonyl)-DGJ (compounds 24) also led to a loss of activity in these assays. The aminocyclopentitols N-(n-butyl)- (35 a), N-(n-nonyl)-4-amino-5-(hydroxymethyl)cyclopentane- (35 b), and N-(1-(pentyloxy)methyl)adamantan-1-yl)-1,2,3-triol (35 f), were found to be selective inhibitors of GBA1 and GBA2 that did not inhibit CGT (>1 mm), with the exception of 35 f, which inhibited CGT with an IC50 value of 1 mm. The N-butyl analogue 35 a was 100-fold selective for inhibiting GBA1 over GBA2 (Ki values of 32 nm and 3.3 μm for GBA1 and GBA2, respectively). The N-nonyl analogue 35 b displayed a Ki value of ?14 nm for GBA1 inhibition and a Ki of 43 nm for GBA2. The N-(1-(pentyloxy)methyl)adamantan-1-yl) derivative 35 f had Ki values of ≈16 and 14 nm for GBA1 and GBA2, respectively. The related N-bis-substituted aminocyclopentitols were found to be significantly less potent inhibitors than their mono-substituted analogues. The aminocyclopentitol scaffold should hold promise for further inhibitor development.

A novel O-fucosylation strategy preactivated by (p-Tol)2SO/Tf2O and its application for the synthesis of Lewis blood group antigen Lewisa

Based on a preactivation strategy using (p-Tol)2SO/Tf2O, a new O-fucosylation method with thioglycoside as donor under mild conditions was reported. High yields and excellent α-stereoselectivities of the fucosylation were obtained wi