H. Schene, H. Waldmann
FULL PAPER
By this procedure the following compounds were prepared (for
yields and anomeric ratios see Tables 1Ϫ3).
H), 3.64 (t, J3a,4a ϭ J4a,5a ϭ 9.4 Hz, 1 H, 4a-H), 3.42 (s, 3 H,
OCH3), 2.87 (br. s, 1 H, 3a-OH). Ϫ 125 MHz 13C NMR (CDCl3):
δ ϭ 138.76Ϫ137.16 (C-ipso), 129.15Ϫ126.39 (25 C, Ph), 102.03
(CH-Ph), 98.26 (C-1a), 96.48 (C-1b), 81.65 (C-5b), 81.3 (C-4a),
79.58, 77.22 (C-2a, 2b), 77.64 (C-4b), 70.63, 69.31 (C-3a, 3b), 62.07
(C-5a) 75.64, 75.12, 73.47, 73.17 (4 и CH2Ph), 69.06, 68.37 (C-6a,
6b), 55.35 (CH3). Ϫ C48H52O11 (804.9): calcd. C 71.62, H 6.51;
found C 71.74, H 6.63.
6-O-(2,3,4,6-Tetra-O-benzyl-Ͱ/β--glucopyranosyl)-1,2:3,4-di-O-
isopropylidene-Ͱ--galactopyranoside[11] (10)
Methyl 6-O-(2,3,4,6-Tetra-O-benzyl-Ͱ/β--glucopyranosyl)-(1Ǟ6)-
2,3,4-tri-O-benzyl-Ͱ--glucopyranoside[9] (11)
Methyl 4-O-(2,3,4,6-Tetra-O-benzyl-Ͱ/β--glucopyranosyl)-(1Ǟ4)-
2,3,6-tri-O-benzyl-Ͱ--glucopyranoside[7] (12)
[1]
R. A. Dwek, Chem. Rev. 1996, 96, 683Ϫ720. Ϫ A. Varki, Glyco-
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Cholesteryl 2,3,4,6-Tetra-O-benzyl-Ͱ/β--glucopyranoside[7] (13)
[2]
Reviews on glycoside synthesis: H. Paulsen, Angew. Chem.
Methyl 3-O-(2,3,4,6-Tetra-O-benzyl-Ͱ/β--glucopyranosyl)(1Ǟ3)-
4,5-di-O-benzylidene-Ͱ--glucopyranoside (14a): Rf ϭ 0.19 (n-hex-
1982, 94, 184Ϫ201; Angew. Chem. Int. Ed. Engl. 1982, 21,
155Ϫ172. Ϫ R. R. Schmidt, Angew. Chem. 1986, 98, 213Ϫ236;
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107, 453Ϫ474 and 569Ϫ593; Angew. Chem. Int. Ed. Engl. 1995,
34, 412Ϫ433 and 521Ϫ545.
20
ane/ethyl acetate, 2:1). Ϫ [α]D ϭ ϩ92.4 (c ϭ 0.6, CHCl3 for the
α anomer). Ϫ 500 MHz 1H NMR (CDCl3) (α): δ ϭ 7.10Ϫ6.91 (m,
25 H, Ph-H), 5.49 (s, 1 H, CH-Ph), 5.40 (d, J1b,2b ϭ 3.9 Hz, 1 H,
1b-H), 5.00 (d, J ϭ 10.9 Hz, 1 H, OCH2-Ph) 4.83Ϫ4.78 (m, 3 H,
2 OCH2-Ph, 1a-H), 4.59Ϫ4.45 (m, 4 H, 4 OCH2-Ph), 4.32 (d, J ϭ
12.4 Hz, 1 H, OCH2-Ph), 4.28 (dd, J6aЈ,5a ϭ 4.7 Hz, J6a,6aЈ ϭ 10.3
Hz, 1 H, 6aЈ-H), 4.16 (t, J2a,3a ϭ J3a,4a ϭ 9.4 Hz, 1 H, 3a-H), 4.00
( t, J2b,3b ϭ J3b,4b ϭ 9.3 Hz, 1 H, 3b-H), 3.85 (dt, J5a,6aЈ ϭ 4.6 Hz,
J5a,6a ϭ J5a,4a ϭ 9.9 Hz, 1 H, 5a-H), 3.79Ϫ3.42 (m, 8 H, 2a, 4a,
[3]
Review on the relevance of oligosaccharides to medicinal chem-
istry: J. H. Musser, Ann. Rep. Med. Chem. 1992, 27, 301.
H. Waldmann, G. Böhm, U. Schmid, H. Röttele, Angew. Chem.
[4]
1994, 106, 2024Ϫ2025; Angew. Chem. Int. Ed. Engl. 1994, 33,
1944Ϫ1946. Ϫ G. Böhm, H. Waldmann, Tetrahedron Lett.
1995, 36, 3843Ϫ3846. Ϫ G. Böhm, H. Waldmann, Liebigs Ann.
1996, 613Ϫ619 and 621Ϫ625. Ϫ U. Schmid, H. Waldmann,
Tetrahedron Lett. 1996, 37, 3837Ϫ3840. Ϫ U. Schmid, H. Wald-
mann, Liebigs Ann. 1997, 2573Ϫ2577. Ϫ U. Schmid, H. Wald-
mann, Chem. Eur. J. 1997, 4, 490Ϫ497.
6a, 2b, 4b, 5b, 6b,bЈ-H), 3.40 (s, 3 H, OCH3), 2.52 (d, J2a,OH
ϭ
10.7 Hz, 1 H, 2a-OH). (β anomer): 5.52 (s, 1 H, CH-Ph), 3.42 (s,
3 H, OCH3). Ϫ 125 MHz 13C NMR (CDCl3): δ ϭ 138.93Ϫ137.2
(C-ipso), 129.45Ϫ126.34 (25 C, Ph), (α anomer) 102.21 (CH-Ph),
100.35 (C-1a), 96.49 (C-1b), 81.77, 81.70, 78.75, 77.87, 75.86, 71.19,
69.94, 62.46 (C-2a, 3a, 4a, 5a, 2b, 3b, 4b, 5b), 75.69, 74.98, 73.63,
71.07 (4 CH2Ph), 69.15 (C-6a, 6b), 55.51 (CH3); (β anomer) 103.25
(CH-Ph), 101.49 (C-1b), 99.84 (C-1a), 82.2, 85.18, 80.81, 79.11,
78.01, 75.13, 72.68, 62.96 (C-2a, 3a, 4a, 5a, 2b, 3b, 4b, 5b), 75.6,
75.37, 73.7 (4 и CH2Ph), 69.0, 68.85 (C-6a, 6b), 55.39 (CH3). Ϫ
C48H52O11 (804.9): calcd. C 71.62, H 6.51; found C 71.81, H 6.64.
[5]
Recent review: A. Flohr, H. Waldmann, J. Prakt. Chem. 1995,
337, 609Ϫ611.
[6]
T. J. Martin, R. R. Schmidt, Tetrahedron Lett. 1992, 33,
6123Ϫ6126. Ϫ T. Müller, R. Schneider, R. R. Schmidt, ibid.
1994, 35, 4763Ϫ4766. Ϫ M. M. Sim, H. Kondo, C.-H. Wong,
J. Am. Chem. Soc. 1993, 115, 2260Ϫ2267. Ϫ Y. Watanabe, C.
Nakamoto, S. Ozaki, Synlett 1993, 115Ϫ116. Ϫ T. Müller, G.
Hummel, R. R. Schmidt, Liebigs Ann. Chem. 1994, 325Ϫ329.
Ϫ S. Hashimoto, K. Umeo, N. Watanabe, M. Nakajima, S. Ike-
gami, Tetrahedron Lett. 1995, 36, 2251Ϫ2254.
[7]
Y. Watanabe, C. Nakamoto, T. Yamamoto, S. Ozaki, Tetra-
Methyl 2-O-(2,3,4,6-Tetra-O-benzyl-Ͱ--glucopyranosyl)-(1Ǟ2)-
4,5-di-O-benzylidene-Ͱ--glucopyranoside (14b): Rf ϭ 0.33 (n-hex-
ane/ethyl acetate, 2:1). Ϫ [α]D20 ϭ ϩ160.8 (c ϭ 0.1, CHCl3). Ϫ 500
MHz 1H NMR (CDCl3): δ ϭ 7.5Ϫ7.1 (m, 25 H, Ph-H), 5.52 (s,
1Η,CH-Ph), 4.97 (d, J ϭ 10.9 Hz, 1 H, OCH2-Ph), 4.93 (d, J1a,2a ϭ
3.7 Hz, 1 H, 1a-H), 4.84 (d, J1b,2b ϭ 4.3 Hz, 1 H, 1b-H), 4.84Ϫ4.43
(m, 7 H, OCH2-Ph), 4.28 (dd, J6aЈ,5a ϭ 4.8 Hz, J6a,6aЈ ϭ 10.1 Hz,
1 H, 6aЈ-H ), 4.13 (t, J3a,2a ϭ J3a,4a ϭ J3b,2b ϭ J3b,4b ϭ 9.2 Hz, 2
H, 3a, 3b-H), 4.04 (t, J4b,5b ϭ J5b,6b ϭ 9.3 Hz, 1 H, 5b-H), 3.85
(dt, J5a,6aЈ ϭ 4.8 Hz, J5a,4a ϭ J5a,6a ϭ 10.1 Hz, 1 H, 5a-H),
3.75Ϫ3.61 (m, 4 H, 6b, 6bЈ, 6a, 4a-H), 3.61Ϫ3.58 (m, 2 H, 2a, 2b-
hedron 1994, 50, 6523Ϫ6536.
[8]
S. Hashimoto, K. Umeo, A. Sano, N. Watanabe, M. Nakajima,
S. Ikegami, Tetrahedron Lett. 1995, 36, 2251Ϫ2254.
[9]
H. Kondo, S. Aoki, Y. Ichikawa, R. L. Halcomb, H. Ritzen,
C.-H. Wong, J. Org. Chem. 1994, 59, 864Ϫ877.
[10]
R. R. Schmidt, M. Behrendt, A. Toepfer, Synlett 1990,
694Ϫ696. Ϫ Y. D. Vankar, P. S. Vankar, M. Behrendt, R. R.
Schmidt, Tetrahedron 1991, 47, 9985Ϫ9992. Ϫ T. J. Martin, R.
Brescello, A. Toepfer, R. R. Schmidt, Glycoconjugate J. 1993,
10, 16Ϫ25.
[11]
H.-W. Liu, K. Nakanishi, J. Am. Chem. Soc. 1982, 104,
1178Ϫ1185.
[97412]
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Eur. J. Org. Chem. 1998, 1227Ϫ1230