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Volumn , Issue 27, 2008, Pages 4607-4614

InCl3-catalyzed rapid 1,3-alkoxy migration in glycal ethers: Stereoselective synthesis of unsaturated α-O-glycosides and an α,α-(1→1)-linked disaccharide

Author keywords

Carbohydrates; Disaccharides; Glycosides; Glycosylation; Lewis acids

Indexed keywords


EID: 53849119888     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200800453     Document Type: Article
Times cited : (21)

References (58)
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    • For very recent reviews on glycosylation methods see: a
    • For very recent reviews on glycosylation methods see: a) A. F. G. Bonget, A. V. Demchenko, Carbohydr. Res. 2007, 342, 374-406;
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    • For palladium-catalyzed transformations of carbonates of 2-C-hydroxymethyl glycals to 2-C-methylene-O-glycosides see: S. Bouoit, C. Goux, D. Sinou, Carbohydr. Lett. 1997, 2, 267-272.
    • For palladium-catalyzed transformations of carbonates of 2-C-hydroxymethyl glycals to 2-C-methylene-O-glycosides see: S. Bouoit, C. Goux, D. Sinou, Carbohydr. Lett. 1997, 2, 267-272.
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    • 3-catalyzed Ferrier-type rearrangement of 2-C-(propargyloxy)-methylglycals see: S. Kashyap, S. R. Vidadala, S. Hotha, Tetrahedron Lett. 2007, 48, 8960-8962.
    • 3-catalyzed Ferrier-type rearrangement of 2-C-(propargyloxy)-methylglycals see: S. Kashyap, S. R. Vidadala, S. Hotha, Tetrahedron Lett. 2007, 48, 8960-8962.
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    • One difficulty often encountered by us is the purification of 2-C-(acetoxylmethyl)-glycals 3. They tend to rearrange or decompose during chromatographic purification over silica gel, sometimes resulting in poor yields. If purified very carefully, they do not have shelf-lives of more than a couple of days even at low temperatures; see also ref. 16.
    • One difficulty often encountered by us is the purification of 2-C-(acetoxylmethyl)-glycals 3. They tend to rearrange or decompose during chromatographic purification over silica gel, sometimes resulting in poor yields. If purified very carefully, they do not have shelf-lives of more than a couple of days even at low temperatures; see also ref. 16.
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    • Such a rearrangement on furanose-derived 2-C-(acetoxymethyl)- glycals has already been reported. See: a) J.Wolf, C. Monneret, R. Pontikis, J.-C. Florent, Eur. J. Org. Chem. 1998, 2417-2423;
    • Such a rearrangement on furanose-derived 2-C-(acetoxymethyl)- glycals has already been reported. See: a) J.Wolf, C. Monneret, R. Pontikis, J.-C. Florent, Eur. J. Org. Chem. 1998, 2417-2423;
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    • Irradiation of the signal at δ = 5.10 ppm due to H-1 of 8a resulted in an enhancement of the signal due to one of the exo-methylene olefinic protons at δ = 5.28 ppm and vice versa. This confirms that that anomeric proton of 8a is in the equatorial position and that the methoxy group is in the axial position. For details of the assignment of anomeric configurations of similar compounds by NOE experiments, see: N. G. Ramesh, K. K. Balasubramanian, Tetrahedron 1995, 51, 255-272.
    • Irradiation of the signal at δ = 5.10 ppm due to H-1 of 8a resulted in an enhancement of the signal due to one of the exo-methylene olefinic protons at δ = 5.28 ppm and vice versa. This confirms that that anomeric proton of 8a is in the equatorial position and that the methoxy group is in the axial position. For details of the assignment of anomeric configurations of similar compounds by NOE experiments, see: N. G. Ramesh, K. K. Balasubramanian, Tetrahedron 1995, 51, 255-272.
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    • Unlike the 2-C-(acetoxymethyl)-glycals 3, all ethers 6a-g, 7a-c reported in this manuscript are relatively stable and can be stored in a refrigerator for longer times.
    • Unlike the 2-C-(acetoxymethyl)-glycals 3, all ethers 6a-g, 7a-c reported in this manuscript are relatively stable and can be stored in a refrigerator for longer times.
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    • While our work was in progress, 2-C-(propargyloxymethyl)-galactal (6d) was reported by Hotha et al, see ref. 14
    • While our work was in progress, 2-C-(propargyloxymethyl)-galactal (6d) was reported by Hotha et al.; see ref. 14.
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    • Alcohols 4 and 5 were each prepared in two steps from the readily available tri-O-benzyl-D-galactal and tri-O-benzyl-D-glucal, respectively, by Vilsmeier-Haack formylation followed by reduction. See: N. G. Ramesh, K. K. Balasubramanian, Tetrahedron Lett. 1991, 32, 3875-3878 and also refs. 11-14, 19.
    • Alcohols 4 and 5 were each prepared in two steps from the readily available tri-O-benzyl-D-galactal and tri-O-benzyl-D-glucal, respectively, by Vilsmeier-Haack formylation followed by reduction. See: N. G. Ramesh, K. K. Balasubramanian, Tetrahedron Lett. 1991, 32, 3875-3878 and also refs. 11-14, 19.
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    • 3-promoted rearrangements of epoxides to carbonyl compounds: B. C. Ranu, U. Jana, J. Org. Chem. 1998, 63, 8212-8216.
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    • th St, Gainesville, FL 32601, USA. The minimum energies reported for compound 6a and cation II were based on conformational search
    • th St., Gainesville, FL 32601, USA. The minimum energies reported for compound 6a and cation II were based on conformational search.
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    • For some very recent reports on the synthesis and structural aspects of trehalose analogues see: a
    • For some very recent reports on the synthesis and structural aspects of trehalose analogues see: a) H.-M. Kim, Y.-K. Chang, S.-I. Ryu, S.-G. Moon, S.-B. Lee, J. Mol. Catal. B 2007, 49, 98-103;
    • (2007) J. Mol. Catal. B , vol.49 , pp. 98-103
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    • Guthrie et al. obtained an anomeric mixture of 14 under the conditions reported by Descotes in ref. 27. Please see: R. D. Guthrie, R. W. Irvine, Carbohyr. Res. 1980, 82, 225-236.
    • Guthrie et al. obtained an anomeric mixture of 14 under the conditions reported by Descotes in ref. 27. Please see: R. D. Guthrie, R. W. Irvine, Carbohyr. Res. 1980, 82, 225-236.
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    • For the synthesis of 14 by a Ferrier-type rearrangement, see: a S. Kashyap, S. Hotha, Tetrahedron Lett. 2006, 47, 2021-2023;
    • For the synthesis of 14 by a Ferrier-type rearrangement, see: a) S. Kashyap, S. Hotha, Tetrahedron Lett. 2006, 47, 2021-2023;
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    • 3-catalyzed Ferrier-type rearrangement of an allylic carbonate to 15, within 2 min under microwave irradiation at 150°C, see H.-C. Lin, C.-C. Chang, J.-Y. Chen, C.-H. Lin, Tetrahedron Asymm. 2005, 16, 297-301.
    • 3-catalyzed Ferrier-type rearrangement of an allylic carbonate to 15, within 2 min under microwave irradiation at 150°C, see H.-C. Lin, C.-C. Chang, J.-Y. Chen, C.-H. Lin, Tetrahedron Asymm. 2005, 16, 297-301.


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