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Y. Du et al. / Tetrahedron Letters 44 (2003) 6887–6890
J 1.5, 12.9 Hz, H-5aI), 3.82, 3.83 (2 s, 6 H, 2 CH3O), 3.86
4.11 (dd, 1 H, J 7.1, 9.2 Hz, H-2I), 4.15 (dd, 1 H, J 2.4,
12.4 Hz, H-6aIII), 4.30 (dd, 1 H, J 5.0, 12.4 Hz, H-6bIII),
(dd, 1 H, J 3.2, 12.9 Hz, H-5bI), 4.28 (dd, 1 H, J 6.7, 9.6
Hz, H-2I), 4.68–4.73 (m, 1 H, H-5II), 5.06 (s, 2 H,
4.70–4.75 (m, 1 H, H-5II), 5.14–5.20 (m, 3 H, H-2III
,
MeOPhCH2), 5.08, 5.12 (2 d,
2
H,
J
12.8 Hz,
H-4III, H-3I), 5.23 (br s, 1 H, H-4I), 5.29 (d, 1 H, J 1.3
Hz, H-1II), 5.31 (d, 1 H, J 8.4 Hz, H-1III), 5.34 (t, 1 H, J
9.3 Hz, H-3III), 5.56–5.59 (m, 2 H, J 7.1, 1.3, 3.6 Hz, H-1I
and H-2II), 5.69 (t, 1 H, J 10.0 Hz, H-4II), 5.96 (dd, 1 H,
J 3.6, 10.0 Hz, H-3II), 6.85 (d, 1 H, J 2.1 Hz, H-6),
7.10–8.11 (m, 19 H, H-8, H-5%, H-2%, H-6% and Ar).
MALDITOF-MS Calcd for C71H68O32: 1432.4; Found
1455.3 (M+Na)+. 1: [h]D25 −129° (c 1, MeOH); 1.07 (d, 1
H), 3.35–3.55 (m, 6 H), 3.68–3.95 (m, 8 H), 4.12 (dd, 1 H,
J 6.3, 7.4 Hz, H-2II), 5.06 (d, 1 H, J 8.0 Hz, H-1III), 5.10
(br s, 1 H, H-1II), 5.59 (d, 1 H, J 6.3 Hz, H-1I), 6.48, 6.74
(2 d, 2 H, J 1.6 Hz, H-6, H-8), 6.90 (d, 1 H, J 8.3 Hz,
H-5%), 7.59 (dd, 1 H, J 2.0, 8.3 Hz, H-6%), 7.66 (d, 1 H, J
2.0 Hz, H-2%); 13C NMR (CD3OD): 17.4, 62.1, 65.5, 68.5,
70.0, 71.2, 72.3 (2 C), 73.0, 74.0, 74.5, 77.1, 77.8, 78.2,
96.2, 100.9, 101.3, 101.8, 102.4, 107.5, 116.4, 117.0, 123.1
(2 C), 135.5, 146.1, 150.0, 157.9, 158.6, 163.0, 164.8,
179.7. MALDITOF-MS Calcd for C32H38O20: 742.2;
Found 765 (M+Na)+, 781 (M+K)+.
MeOPhCH2), 5.20 (dd, 1 H, J 9.6, 3.5 Hz, H-3I), 5.25–
5.28 (m, 1 H, H-4I), 5.35 (d, 1 H, J 1.1 Hz, H-1II), 5.60
(dd, 1 H, J 1.1 Hz, H-2II), 5.66 (t, 1 H, J 9.6 Hz, H-4II),
5.73 (br s, 1 H, 3%-OH), 5.76 (d, 1 H, J 6.7 Hz, H-1I), 5.97
(dd, 1 H, J 3.3, 9.6 Hz, H-4II), 6.45 (d, 1 H, J 2.1 Hz,
H-6), 6.50 (d, 1 H, J 2.1 Hz, H-8), 6.92–6.96 (m, 4 H,
Ar), 7.02 (d, 1 H, J 9.5 Hz, H-5%), 7.23–7.60 (m, 13 H,
Ar), 7.67 (dd, 1 H, J 2.0, 9.5 Hz, H-6%), 7.84–8.10 (m, 7
H, H-2% and Ar), 12.65 (s, 1 H, 5-OH). MALDITOF-MS
Calcd for C67H60O22: 1216.36; Found 1239 (M+Na)+. 16:
1.26 (d, 3 H, J 6.3 Hz, H-6II), 2.07, 2.23, 2.28, 2.50 (4 s,
12 H, 4 Ac), 3.66 (dd, 1 H, J 1.0, 12.4 Hz, H-5aI), 3.85
(dd, 1 H, J 2.1, 12.4 Hz, H-5bI), 4.24 (dd, 1 H, J 7.0, 9.3
Hz, H-2I), 4.78, 4.85 (m, 1 H, H-5II), 5.22 (dd, 1 H, J 3.5,
9.3 Hz, H-3I), 5.27 (br s, 1 H, H-4I), 5.37 (d, 1 H, J 1.0
Hz, H-1II), 5.63 (dd, 1 H, J 1.0, 3.3 Hz, H-2II), 5.71 (d, 1
H, J 7.0 Hz, H-1I), 5.73 (t, 1 H, J 10.1 Hz, H-4II), 6.02
(dd, 1 H, J 3.3, 10.1 Hz, H-3II), 6.37 (d, 1 H, J 1.9 Hz,
H-6), 6.50 (d, 1 H, J 1.9 Hz, H-8), 6.62 (d, 1 H, J 8.4 Hz,
H-5%), 7.24–8.13 (m, 17 H, H-2%,6% and Ar). MALDITOF-
MS Calcd for C55H48O22: 1060.26; Found 1083 (M+Na)+.
18: [h]2D5 −38° (c 1.6, CHCl3); 1.15 (d, 3 H, 6.3 Hz, H-6II),
2.03, 2.05, 2.06, 2.07, 2.08, 2.21, 2.27, 2.34, 2.47 (9 s, 27
H, 9 Ac), 3.55 (dd, 1 H, J 1.0, 12.9 Hz, H-5aI), 3.78 (dd,
1 H, J 3.0, 12.9 Hz, H-5bI), 3.91–3.94 (m, 1 H, H-5III),
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