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LETTER
(16) (a) Wada, T.; Ohkubo, A.; Mochizuki, A.; Sekine, M.
Tetrahedron Lett. 2001, 42, 1069. (b) Love, K. R.; Andrade,
R. B.; Seeberger, P. H. J. Org. Chem. 2001, 66, 8165.
(17) Byramova, N. E.; Ovchinnikov, M. V.; Bakinovskii, L. V.;
Kochetkov, N. K. Carbohydr. Res. 1983, 124, C8.
(18) Jiang, L.; Chan, T.-H. J. Org. Chem. 1998, 63, 8035.
(19) (a) Magand, D.; Grandjean, C.; Doutheau, A.; Anker, D.;
Shevchik, V.; Cotte-Pattat, N.; Robert-Baudouy, J.
5.27 (s, 1 H), 5.18 (t, J = 9.2 Hz, 1 H), 5.13 (d, J = 7.7 Hz, 1
H), 4.68 (dd, J = 11.8, 3.7 Hz, 1 H), 4.61–4.45 (m, 4 H), 4.27
(m, 1 H), 4.11 (m, 1 H), 4.04 (t, J = 8.1 Hz, 1 H), 3.88 (m, 1
H), 3.75–3.65 (m, 2 H), 3.38 (m, 1 H), 3.10 (m, 1 H), 2.80
(m, 1 H), 1.11, 0.97, 0.87, 0.84, 0.78, 0.70, 0.43 (7 × s, 3 H
each). 13C NMR (75 MHz, CDCl3): d = 175.7, 167.0, 166.15,
166.07, 165.6, 165.2, 165.1, 164.7, 143.0, 133.9, 133.4,
133.2, 133.0, 129.8, 129.6, 129.0, 128.7, 128.3, 128.2,
122.7, 103.3, 100.8, 91.9, 90.7, 79.4, 75.1, 72.9, 72.0, 70.3,
70.1, 69.4, 63.4, 62.7, 62.4, 55.4, 47.4, 46.8, 45.7, 41.5, 40.9,
39.1, 38.9, 38.4, 36.5, 33.7, 32.9, 31.7, 30.5, 29.6, 27.8, 26.1,
25.4, 23.4, 23.3, 22.6, 18.0, 16.4, 16.3, 15.1. HRESI–MS:
m/z [M + Na]+ calcd for C111H114O27Na: 1901.7440; found:
1901.7436. 20: [a]D = 44.4 (c 0.7, CHCl3). 1H NMR (300
MHz, CDCl3): d = 8.02–7.80 (m, 13 H), 7.78–7.71 (m, 4 H),
7.64–7.19 (m, 28 H), 6.00 (t, J = 9.6 Hz, 1 H), 5.96 (d, J =
7.7 Hz, 1 H), 5.78–5.68 (m, 3 H), 5.64 (t, J = 9.5 Hz, 1 H),
5.44 (t, J = 8.4 Hz, 1 H), 5.27 (s, 1 H), 5.25–5.11 (m, 2 H),
4.75–4.62 (m, 2 H), 4.60–4.44 (m, 3 H), 4.28 (m, 1 H), 4.18–
3.95 (m, 4 H), 3.58–2.92 (br s, 1 H), 3.12 (m, 1 H), 2.79 (m,
1 H), 1.26, 1.00, 0.86, 0.84, 0.71, 0.68, 0.42 (7 × s, 3 H each).
13C NMR (75 MHz, CDCl3): d = 175.6, 166.1, 165.6, 165.2,
165.1, 164.7, 142.9, 133.4, 133.0, 129.8, 129.6, 128.6,
128.3, 128.2, 122.7, 102.9, 100.5, 91.9, 91.0, 72.9, 72.0,
70.3, 69.9, 69.3, 63.4, 62.7, 55.3, 47.3, 46.8, 45.7, 41.5, 40.9,
38.9, 38.8, 38.3, 36.4, 33.7, 32.9, 31.7, 30.5, 29.6, 27.8, 25.4,
23.4, 22.6, 18.0, 16.4, 16.2, 15.1. HRESI–MS: m/z [M +
Na]+ calcd for C111H112O28Na: 1915.7232; found:
Carbohydr. Res. 1998, 314, 189. (b) Karst, N.; Jacquinet, J.-
C. Eur. J. Org. Chem. 2002, 815.
(20) All compounds involved in the synthesis have been well
characterized. Selected data for 18–20 and 1 are herewith
listed. 18: [a]D = 43.8 (c 1.0, CHCl3). 1H NMR (300 MHz,
CDCl3): d = 8.25 (d, J = 7.7 Hz, 4 H), 7.99 (d, J = 7.1 Hz, 2
H), 7.92–7.80 (m, 7 H), 7.72 (t, J = 8.8 Hz, 4 H), 7.66–7.18
(m, 28 H), 6.00 (t, J = 9.6 Hz, 1 H), 5.96 (d, J = 8.2 Hz, 1 H),
5.78 (dd, J = 9.6, 8.4 Hz, 1 H), 5.71 (t, J = 9.6 Hz, 1 H), 5.66
(t, J = 9.3 Hz, 1 H), 5.58 (t, J = 9.4 Hz, 1 H), 5.41 (dd, J =
9.3, 9.1 Hz, 1 H), 5.39 (t, J = 9.1 Hz, 1 H), 5.26 (s, 1 H), 5.12
(t, J = 9.6 Hz, 1 H), 5.02 (d, J = 7.7 Hz, 1 H), 4.67 (dd, J =
12.1, 3.6 Hz, 1 H), 4.61–4.53 (m, 2 H), 4.52–4.43 (m, 2 H),
4.30–4.19 (m, 2 H), 4.13–4.01 (m, 3 H), 3.68 (m, 1 H), 3.08
(dd, J = 4.5, 3.1 Hz, 1 H), 2.79 (m, 1 H), 2.05, 1.76, 1.09,
0.97, 0.86, 0.84, 0.76, 0.69, 0.43 (9 × s, 3 H each). 13C NMR
(75 MHz, CDCl3): d = 175.7, 170.6, 169.5, 166.2, 165.7,
165.1, 164.8, 143.1, 133.6, 133.5, 133.3, 133.2, 133.0,
129.8, 129.6, 129.2, 128.9, 128.7, 128.3, 122.7, 103.3,
100.6, 91.9, 90.9, 75.3, 72.9, 72.0, 71.1, 70.4, 70.1, 69.4,
68.9, 63.4, 62.8, 62.4, 55.4, 47.4, 46.8, 45.7, 41.5, 41.0, 39.1,
38.9, 38.4, 36.5, 33.7, 33.0, 31.7, 30.5, 29.7, 27.8, 25.8, 25.5,
23.5, 23.3, 22.6, 20.7, 20.4, 18.0, 16.4, 16.3, 15.2. HRESI–
MS: m/z [M + Na]+ calcd for C115H118O29Na: 1985.7651;
found: 1985.7643. 19: [a]D = 51.1 (c 1.0, CHCl3). 1H NMR
(300 MHz, CDCl3): d = 8.05–7.82 (m, 13 H), 7.76–7.71 (m,
4 H), 7.64–7.16 (m, 28 H), 6.01 (t, J = 9.6 Hz, 1 H), 5.96 (d,
J = 8.0 Hz, 1 H), 5.76 (dd, J = 9.6, 8.4 Hz, 1 H), 5.71 (t, J =
9.6 Hz, 1 H), 5.67–5.61 (m, 2 H), 5.53 (t, J = 8.7 Hz, 1 H),
1915.7197. 1: [a]D = 3 (c 0.35, MeOH) {lit.1: [a]D = 2.85
(MeOH)}. 13C NMR (100 MHz, C5D5N): d = 177.9, 144.9,
126.0, 105.6, 105.4, 96.3, 90.7, 81.8, 78.9, 78.5, 78.3, 78.1,
77.0, 74.4, 73.9, 72.3, 71.6, 63.4, 62.7, 56.6, 48.7, 47.9, 47.0,
42.8, 42.4, 40.6, 40.3, 39.5, 37.6, 34.7, 33.9, 33.2, 31.5, 30.6,
28.9, 28.8, 26.8, 24.4, 19.2, 18.2, 17.4, 16.2. HRESI–MS:
m/z [M+ Na]+ calcd for C48H76O19Na: 979.4873; found:
979.4907.
Synlett 2004, No. 2, 259–262 © Thieme Stuttgart · New York