Mannopyranoside methyl 6-0-tosyl

Stannylene-mediated glycosylation was first applied to alkyl mannosylations. Condensation of the stannylene acetal of 3,4,6-tri-O-benzyImannopyranose (44) with methyl iodide and allyl bromide in DMF afforded the desired methyl and allyl P-mannopyranosides, respectively, in almost quantitative yields [20]. Benzyl p-mannopyranoside was obtained from the same stannylene acetal by use of BU4NI in benzene [21]. The electrophilic leaving group is responsible for the reactivity and stereoselectivity. Methylation with methyl tosylate and dimethyl sulfate gave methyl mannopyranosides as anomeric mixtures at temperatures above 75 °C [20]. 

In 1938, Lake and Peat168 reported that methyl 2,3-anhydro-4,6-dimethyl-/3-D-mannopyranoside (prepared from methyl 2-tosyl-3,4,6-triacetyl- S-D-glucopyranoside by detosylation with sodium methoxide and subsequent methylation)164 gave rise, when boiled with sodium methoxide in methyl alcohol, to almost equal proportions of methyl... 

It was claimed308 that alkaline hydrolysis of methyl 6-deoxy-2,3-0-isopropylidene-4-O-tosyl-n-mannoside (I) gives, by Walden inversion at carbon atom 4, methyl 6-deoxy-2,3-0-isopropylidene-L-talopyranoside (II) and that alkaline hydrolysis of methyl 6-deoxy-2,3-0-isopropylidene-5-0-tosyl-L-mannoside (III) yields,308 by inversion at carbon atom 5, methyl 6-deoxy-2,3-0-isopropylidene-D-gulofuranoside (IV) plus methyl 6-deoxy-2,3-0-isopropylidene-L-mannosid-5,6-een (C). The formation of C has since been confirmed,380 but IV was shown to be800 307 actually methyl 6-deoxy-2,3-O-isopropylidene-L-mannofuranoside (B), and II is indeed methyl 6-deoxy-2,3-0-isopropylidene-L-mannopyranoside (A). Thus, this claim to discovery... 

One of the most prominent papers to come from the Aspinall group, published with George Zweifel in 1957, reported on the selective tosylation of the 2,3-diols of methyl 4,6-O-benzyl idene-a-D-mannopyranoside (with axial and equatorial hydroxyl groups, respectively, at C-2 and C-3), and 1,6-anhydro-/i-D-mannopyranose (with a confor-mationally inverted pyranose chair, and therefore with equatorial and axial hydroxyl groups, respectively, at C-2 and C-3). In each case the equatorial hydroxyl group was esterified preferentially, consistent with the Barton/Cookson generalization,... 

Triphenyltin lithium has been used to open the oxiran rings of methyl 2,3-anhydro-4,6-0-benzylidene-a-D-allo- and -mannopyranosides to give the tin-bonded altrosides (10) and (11) in 75 and 94% yield respectively. A 43% yield of the C-6 bonded tin derivative (12) was obtained by using the reagent to displace the corresponding tosylate. The n.m.r. of these products is reported in Chapter 20." ... 

From a study of the partial tosylation of methyl <-D-mannopyranoside, the order of substitution was found to be 6>3>2>4. With two equi-... 

Me glycoside, 4-tosyl Methyl 2,3-di-O-methyl-4-O-tosyl-a-D-mannopyranoside [32934-13-7]... 

Tosyl Methyl 4,6-0-ethylidene-2-0-tosyl-a-D-mannopyranoside C16H22O8S 374.411... 

Tri-Ac, 3-tosyl Methyl 2,4,6-tri-O-acetyl-3-O-tosyl-oc-D-mannopyranoside C20H26O11S 474.485... 

Tosyl Methyl 2-0-tosyl-6-0-trityl-a-D-mannopyranoside Md +6 (c, 5.6 in CHCI3). 

Me glycoside, 2-tosyl Methyl 3,4,6-tri-O-methyl-2-O-tosyl-a-D-mannopyranoside [53008-58-5]... 

Benzyl 2,3-0-isopropylidene-a-D-lyxofuranoside, 1-70 Benzyl 2,3-0-isopropylidene-p-D-lyxofuranoside, L-72 Benzyl 2,3-0-isopropylidene-a-D-mannofuranoside, B-19 Benzyl 2,3-0-isopropylidene-a-D-mannopyranoside, B-19 Benzyl 2,3-0-isopropylidene-5-0-mesyl-a-D-lyxofuranoside, 1-70 Benzyl 2,3-0-isopropylidene-6-0-mesyl-a-D-mannofuranoside, B-19 Benzyl 2,3-0-isopropylidene-4-0-mesyl-a-L-rhamnopyranoside, B-20 Benzyl 3,4-0-isopropylidene-2-C-methyl-p-L-arabinopyranoside, M-229 Benzyl 3,4-0-isopropylidene-2-C-methyl-p-L-ribopyranoside, M-286 Benzyl 3,4-0-isopropylidene-2-0-methyl-p-D-ribopyranoside, B-21 Benzyl 3,4-0-isopropylidene-2-0-methyl-p-L-ribopyranoside, B-21 Benzyl 3,4-0-isopropylidene-p-D- /7// ro-pentopyranosid-2-ulose, P-42 Benzyl 2,3-0-isopropylidene-a-L-rhamnopyranoside, B-20 Benzyl 2,3-0-isopropylidene-p-D-ribofuranuronoside, R-146 Benzyl 3,4-0-isopropylidene-p-D-ribopyranoside, B-21 Benzyl 3,4-0-isopropylidene-p-L-ribopyranoside, B-21 Benzyl 3,4-0-isopropylidene-2-0-(2,3,4,6-tetra-0-acetyl-p-D-glucopyranosyl)-p-D-arabinopyranoside, G-284 Benzyl 2,3-0-isopropylidene-5-0-(2,3,4,6-tetra-0-acetyl-p-D-glucopyranosyl)-p-D-ribofuranoside, G-462 Benzyl 3,4-0-isopropylidene-2-0-tosyl-a-D-arabinopyranoside, B-14 Benzyl 3,4-0-isopropylidene-2-tosyl-p-L-arabinopyranoside, B-14 Benzyl 3,4-0-isopropylidene-2-0-(2,3,5-tri-0-benzoyl-a-L-arabinofuranosyl)-p-L-arabinopyranoside, A-801 Benzyl 3,4-0-isopropylidene-6-0-trityl-p-D-galactopyranoside, B-15... 

Methyl 2-benzamido-2-deoxy-4,6-di- 0 -tosyl-a-D-glucopyranoside, M-154 Methyl 2-benzamido-2-deoxyglucopyranoside, M-154 Methyl 3-benzamido-3-deoxy-a-D-mannopyranoside, A-313 Methyl 2-benzamido-2-deoxy-3-0-mesyl-a-D-glucopyranoside, M-154 Methyl 2-benzamido-2-deoxy-3-0-methyl-p-D-glucopyranoside, M-154 Methyl 2-benzamido-2-deoxy-3,4,6-tri-O -mesyl-a-D-glucopyranoside, M-154 Methyl 2-benzamido-2-deoxy-3,4,6-tri-0-methyl-a-D-glucopyranoside, M-154... 

Methyl 4,6-0-benzylidene-3-0-methyl-a-D-mannopyranoside, M-169 Methyl 4,6-0-benzylidene-3-0-methyl-p-D-mannopyranoside, M-169 Methyl l,3-0-benzyhdene-5-0-methyl-a-L-sorbopyranoside, M-210 Methyl 3,4-0-benzylidene-2-0-methyl-l-thio-(3-L-fucopyranoside, T-63 Methyl 4,6-0-benzylidene-3-0-methyl-2-0-tosyl-a-D-allopyranoside, M-155 Methyl 4,6-0-benzylidene-3-C-methyl-2-0-tosyl-a-D-allopyranoside, M-224 Methyl 4,6-0-benzylidene-3-0-methyl-2-0-tosyl-a-D-altropyranoside,... 

Methyl 2-0-benzyl-3,4-0-isopropylidene-p-L-arabinopyranoside, M-197 Methyl 2-0-benzyl-3,4-O-isopropylidene-a-L-fucopyranoside, M-198 Methyl 3- 0 -benzyl-1,2- O -isopropylidene- p-L-idofuranuronate, 1-12 Methyl 5-0-benzyl-2,3-0-isopropylidene-a-D-lyxofuranoside, 1-70 Methyl 5-O-benzyl-2,3-O-isopropylidene-a-D-mannofuranoside, 1-71 Methyl 6-O-benzyl-2,3-O-isopropylidene-a-D-mannofuranoside, 1-71 Methyl 4-O-benzyl-2,3-O-isopropylidene-a-L-rhamnopyranoside, M-207 Methyl 2-O-benzyl-3,5-O-isopropylidene-a-D-xylofuranoside, M-216 Methyl 2-O-benzyl-3,5-O-isopropylidene-p-D-xylofuranoside, M-216 Methyl 3-0-benzyl-2-0-methyl-a-D-allopyranoside, M-148 Methyl 5-0-benzyl-2-0-methyl-a-D-glucofuranosidurono-6,3-lactone, G-539 Methyl 5-0-benzyl-2-0-methyl-p-D-glucofuranosidurono-6,3-lactone, G-539 Methyl 2,6-0-benzyl-3-0-methyl-a-D-mannopyranoside, M-271 Methyl 3-0-benzyl-2-O-methyl-6-0-tosyl-a-D-allopyranoside, M-148 Methyl 5-0-benzyl-3-0-methyl-a-D-xylofuranoside, M-216 Methyl 3-0-benzyl-a-L-rhamnopyranoside, M-207 Methyl 4-0-benzyl-a-L-rhamnopyranoside, M-207 Methyl 3-0-benzyl-p-L-ribofuranoside, M-208 Methyl 3-O-benzyl-4-O -(2,3,4-tri-O-benzyl-p-D-xylopyranosyl)-p-D-xylopyranoside, X-80... 

Methyl 2,6-di-0-benzoyl-3-0-methyl-p-D-mannopyranoside, M-205 Methyl 3,5-di-0-benzoyl-2-0-methyl-p-D-ribofuranoside, M-208 Methyl 4,6-di-O-benzoyl-2-0-methyl-3-O-tosyl-a-D-altropyranoside, M-149 Methyl 3,5-di-0-benzoyl-p-D-tAreo-pentofuranosid-2-ulose, P-45 Methyl 2,3-di-O-benzoyl-a-L-rhamnopyranoside, M-207 Methyl 2,4-di-O-benzoyl-a-L-rhamnopyranoside, M-207 Methyl 3,5-di-O-benzoyl-p-D-ribofuranoside, M-208 Methyl 2,3-di-O-benzoyl-l-thio-p-L-fucopyranoside, T-63 Methyl 2,3-di-O-benzoyl-l-thio-a-L-rhamnopyranoside, T-86 Methyl 2,3-di-0-benzoyl-5-0-tosyl-a-L-arabinofuranoside, M-152 Methyl 3,5-di-0-benzoyl-2-0-tosyl-p-D-lyxofuranoside, M-201 Methyl 2,3-di-0-benzoyl-4-0-tosyl-a-L-rhamnopyranoside, M-207 Methyl 2,4-di-0-benzoyl-3-0-(2,3,4-tri-0-acetyl-a-L-rhamnopyranosyl)-a-D-xylopyranoside, R-77... 

Methyl 2,3 di-0-methyl-4-0-tosyI-a-D-mannopyranoside, D-748 Methyl 3,4-di-0-methyl-2-0-tosyl-a-D-mannopyranoside, D-751 Methyl 2,3 di-0-methyl-4-0-tosyl-a-L-rhainnopyranoside, M-207 Methyl 3,4-di-0-methyl-2-0-(2,3,4-tri-0-niethyl-p-D-xylopyfanosyl)-p-D-xylopyranoside, X-78... 

Methyl 5-ethenyl-2,2-dimethyl-l,3-dioxolane-4-carboxylate, D-708 Methyl (ethyl 2,3,4-tri-0-benzyl-l-thio-p-D-glucopyranosid)uronate, T-75 Methyl 3,4-0-ethylidene-p-L-arabinopyranoside, M-153 Methyl 4,6-0-ethylidene-2,3-di-0-metiiyl-p-D-galactopyranoside, M-186 Methyl 4,6-0-ethylidene-2,3-di-0-methyl-a-D-niannopyranoside, M-180 Methyl 4,6-0-ethylidene-2,3-di-0-tosyl-a-D-glucopyranoside, M-190 Methyl 4,6-0-ethylidene-2,3-di-0-tosyl-a-D-mannopyranoside, M-180 Methyl 4,6-O-ethylidene-a-D-galactopyranoside, M-185 Methyl 3,4-O-ethylidene-p-D-galactopyranoside, M-186 Methyl 4,6-O-ethylidene-a-D-glucopyranoside, M-190 Methyl 4,6-0-ethylidenemannopyranoside, M-180 Methyl 4,6-0-ethylidene-2-0-methyl-a-D-altropyranoside, M-149 Methyl 4,6- O -ethylidene-2-0 -methyl-a-D-arafeiwo -hexopyranosid-3-ulose, H-95... 

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