Allyl p-D-glucopyranoside

Neda, I, Sakhaii, P, Wassmann, A, Niemeyer, U, Gunther, E, Engel, J, A practical synthesis of benzyl a- and allyl p-D-glucopyranosides regioselectively substituted with (CH2)30H groups stereocon-troUed p-galactosidation by cation ir-interaction. Synthesis, 1625-1632, 1999. 

Methyl-3-O-allyl-P-D-glucopyranoside (1.00 g, 4.27 mmol) assume toxic... 

Methyl (3-0-acetyl-6-deoxy-2,4-di-0-methyl-a-L-galactopyranosyl)-(1->4)-(allyl 2,3-di-Obenzoyl-p-D-glucopyranosid)uronate... 

Reaction of arylboronic acid with allyl-2,3,4,6-tetra-0-acetyl-P-D-glucopyranoside... 

Carbohydrates remain an attractive source of chirality in preparation of ligands for asymmetric catalysis. Functionalized phospholanes, 192 [167], and chiral bisphosphinites 193 [168] with an attached crown ether unit were obtained recently from D-mannitol and from phenyl 2,3-di-0-allyl-4,6-0-benzylidene-p-D-glucopyranoside, respectively (Figure 18). Compounds 194 and 195 were obtained in the photochemical addition of H2P(CH2)3PPH2 onto the crresponding alkenes - Pd-complexes of these new bisphosphines were successfully applied as catalysts in the copolymerization of CO and... 

To a solution of 2-(trimethylsilyl)ethyl 3-O-allyl-6-0-benzyl-2-phthalimido-2-deoxy-p-D-glucopyranoside (250 mg, 0.49 mmol) and 18 p,L of 1M MeOTf solution in 0.5 mL of dry dichloromethane was added dropwise 18.8 mg (0.07 mmol) of 3-methoxy-2-pyridyl p-L-fucopyranoside in 0.5 mL of solvent over 15 min. The mixture was stirred at room temperature for 30 min, and processed as described in the foregoing. The residue was purified by flash chromatography on silica gel column using EtOAc-hexane, (2 1) as eluant to recover the excess of acceptor. Elution of the column with EtOAc-hexane, (1 1) containing 10% methanol gave 20 mg of the title product in 43% yield as a syrup. 

Reaction of benzyl 4-O-benzyl-a-L-talopyranoside [142] and methyl 4,6-O-benzyli-dene-p-D-glucopyranoside [140] was less regioselective, giving 54% and 66%, respectively, of the 3-allyl ethers. No diallyl ethers were formed and no starting material remained, the rest being the isomeric 2-allyl ether. In both cases, tetrabutylammonium bromide was used to catalyze the reaction of the 2,3-O-dibutylstannylene intermediate with allyl bromide. 

Sialylation of allyl 4-0-(3-0-(2-a-N-acetylneuroaminyl)-P-D- C-l-galactopyr-anosyl)-2-acetamido-2-deoxy-P-D-glucopyranoside using an a-2,3-sialyltransferase with in situ regeneration of CMP-NeuAc [41] (Figure 12.18). ... 

Tri-Ac Allyl 2-acetamido-3,4,6-tri-O-acet-yl-2-deoxy-P-D-glucopyranoside C17H25NO9 387.386 Mp 162-163°. Mg -17.4 (CHCI3). 

Allyl 3,4-0-isopropylidene-a-D-glucopyranoside, A-94 Allyl 2,3,4,6-tetra-O-acetyl-p-D-glucopyranoside, A-94 Allyl 2,3,4,6-tetra-O-acetyl-a-D-glucopyranoside, A-94 Allyl 2,3,4-tri-O-benzoyl-a-D-glucopyranoside, A-94... 

Allyl 2-acetamido-3,4,6-tri-0-acetyl-2-deoxy-p-D-glucopyranoside, A-88 Allyl 2-amino-2-deoxy-a-D-glucofuranoside, A-266... 

Allyl 6-0-benzyl-2-deoxy-2-phthalimido-p-D-glucopyranoside, A-266 2-Amino-l,5-anhydro-2-deoxyallitol n-form, A-123... 

Alkylation of metal chelates of sucrose with allyl halides and sodium bromo-acetate in DMSO yielded mono-O-allylated and mono-O-carboxymethylated derivatives. A new acidic monosaccharide from the O-specific lipopolysaccharide of Shigella dysenteriae type 3 has been identified as 4-0-[(/ )-l-carboxy-ethyl]-D-glucopyranose on the basis of chemical and mass-spectral evidence and by its synthesis by alkylation of methyl 2,3,6-tri-0-benzyl-a(P)-D-glucopyranoside with (5)-2-chloropropionic acid, esterification (with diazomethane), hydrogenolysis, and acid hydrolysis. ... 

The carbohydrate mimics 43 and 44 of inositol 1,4,5-trisphosphate have been synthesized in eight steps from allyl a- or P-D-xylopyranoside and allyl o-d-glucopyranoside, respectively, and methyl 2,3,4-trisphospho-a-D-mannopyrano-side has been prepared in three steps from methyl 6-O-trityl-a-D-mannopyrano-side as a mimic of lD-wyo-inositol-trisphosphate, The synthesis of inositol phosphates is covered in Chapter 18. 

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