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300), 3.63 (dd, 1H, J¼10.0, 3.5 Hz, H-400), 3.52 (dd, 1H,
J¼13.5, 2.5 Hz, H-6000a), 3.33–3.46 (m, 8H, H-6000b, 2000,
4000, 500, 600, and –CH2–), 2.86–3.02 (m, 2H, –CH2–), 2.39–
2.45 (m, 1H, H-20), 2.17–2.22 (m, 2H, Heq-200 and H-20),
1.91 (d, 3H, J¼1.0 Hz, 5-CH3), 1.72–1.77 (m, 2H, –CH2–),
1.18 (q, 1H, J¼12.0 Hz, Hax-200); 13C NMR (125 MHz,
CD3OD): d 172.7 (–CO), 166.4 (C-2), 152.5 (C-4), 139.4
(C-6), 111.9 (C-5), 95.5 (C-1000), 88.9 (C-10), 87.5 (C-40),
78.6 (C-30), 76.0 (C-400), 75.5 (C-4000), 73.6 (C-600), 73.1
(C-3000), 72.6 (C-500), 64.9 (C-5000), 60.7 (C-2000), 59.9 (C-
100), 59.7 (C-300), 52.5 (C-6000), 49.5 (–CH2–), 39.3 (C-20),
38.5 (–CH2–), 33.6 (C-200), 31.2 (–CH2–), 12.6 (–CH3).
HRESI-MS Calcd for C25H37N16O10 ([M+H]+): 721.2873,
found: 721.2865.
(m, 2H, –CH2–), 1.24 (q, 1H, J¼13.0 Hz, Hax-200); 13C
NMR (125 MHz, CD3OD): d 172.1 (–CO), 166.4 (C-2),
152.4 (C-4), 139.6 (C-6), 111.8 (C-5), 96.0 (C-1000), 89.2
(C-10), 84.6 (C-40), 78.2 (C-400), 75.0 (C-4000), 73.7 (C-600),
73.3 (C-3000), 72.5 (C-500), 65.2 (C-30), 65.0 (C-5000), 60.6 (C-
2000), 60.1 (C-100), 59.6 (C-300), 52.5 (C-6000), 38.2 (–CH2–),
36.9 (C-20), 33.1 (C-200), 30.5 (–CH2–), 12.5 (–CH3).
HRESI-MS Calcd for C25H36N19O9 ([M+H]+): 746.2938,
found: 746.2926.
3.9.5. Compound 4e. Yield: 88% from 3a, white foam. 1H
NMR (500 MHz, CD3OD): d 5.30 (t, 1H, J¼5.0 Hz, H-10),
5.13 (d, 1H, J¼4.0 Hz, H-1000), 4.51–4.54 (m, 1H, H-30),
4.28 (d, 1H, J¼2.5 Hz, H-40), 3.81–4.03 (m, 4H, H-5000, 3000,
100, and 300), 3.62 (dd, 1H, J¼10.5, 3.5 Hz, H-400), 3.51–
3.54 (m, 4H, H-6000a, OCH3), 3.27–3.47 (m, 7H, H-6000b,
2000, 4000, 500, 600, and –CH2–), 2.98–3.07 (m, 2H, –CH2–),
2.20 (ddd, 1H, J¼13.0, 5.0, 5.0 Hz, Heq-200), 2.03–2.15 (m,
2H, H-20), 1.19 (q, 1H, J¼13.0 Hz, Hax-200); 13C NMR
(125 MHz, CD3OD): d 174.0 (–CO), 109.0 (C-10), 95.6 (C-
1000), 87.5 (C-40), 78.9 (C-30), 75.7 (C-400), 75.5 (C-4000),
73.6 (C-600), 73.2 (C-3000), 72.6 (C-500), 64.9 (C-5000), 60.7
(C-2000), 59.8 (C-100), 59.3 (C-300), 57.2 (–OCH3), 52.5 (C-
6000), 50.4 (–CH2–), 41.3 (C-20), 40.8 (–CH2–), 33.7 (C-200).
HRESI-MS Calcd for C20H33N14O9 ([M+H]+): 613.2550,
found: 613.2547.
3.9.2. Compound 4b. Yield: 85% from 3c, white foam. 1H
NMR (500 MHz, CD3OD): d 7.91 (d, 1H, J¼1.0 Hz, H-6),
6.30 (dd, 1H, J¼9.0, 6.0 Hz, H-10), 5.12 (d, 1H, J¼4.0 Hz,
H-1000), 4.50–4.52 (m, 1H, H-30), 4.28 (d, 1H, J¼2.0 Hz,
H-40), 3.80–4.01 (m, 4H, H-5000, 3000, 100 and 300), 3.63 (dd,
1H, J¼10.0, 3.0 Hz, H-400), 3.52 (dd, 1H, J¼13.5, 2.5 Hz,
H-6000a), 3.25–3.46 (m, 8H, H-6000b, 2000, 4000, 500, 600, and
–CH2–), 2.81–2.98 (m, 2H, –CH2–), 2.39–2.44 (m, 1H, H-
20), 2.19–2.24 (m, 2H, Heq-200 and H-20), 1.90 (d, 1H, J¼
1.0 Hz, –CH3), 1.54–1.65 (m, 4H, –CH2CH2–), 1.19 (q, 1H,
J¼12.0 Hz, Hax-200); 13C NMR (125 MHz, D2O): d 172.7
(–CO), 166.4 (C-2), 152.5 (C-4), 139.6 (C-6), 111.8 (C-5),
95.4 (C-1000), 89.0 (C-10), 87.4 (C-40), 78.7 (C-30), 75.9 (C-
400), 75.5 (C-4000), 73.5 (C-600), 73.0 (C-3000), 72.6 (C-500), 64.8
(C-5000), 60.8 (C-2000), 59.9 (C-100), 59.6 (C-300), 52.5 (C-6000),
51.7 (–CH2–), 40.3 (–CH2–), 39.3 (C-20), 33.6 (C-200), 28.9
(–CH2–), 28.2 (–CH2–), 12.6 (–CH3). HRESI-MS Calcd
for C26H39N16O10 ([M+H]+): 735.3029, found: 735.3051.
3.9.6. Compound 6a. Yield: 68% from 3b, white foam. 1H
NMR (500 MHz, CD3OD): d 8.10 (d, 1H, J¼8.0 Hz, H-6),
5.85 (d, 1H, J¼6.0 Hz, H-10), 5.74 (d, 1H, J¼8.5 Hz, H-5),
5.13 (d, 1H, J¼3.5 Hz, H-1000), 4.43 (dd, 1H, J¼6.0,
5.0 Hz, H-20), 4.37 (d, 1H, J¼3.5 Hz, H-40), 4.24 (dd, 1H,
J¼5.0, 3.5 Hz, H-30), 3.80–4.02 (m, 4H, H-5000, 3000, 100, and
300), 3.65 (dd, 1H, J¼10.0, 3.5 Hz, H-400), 3.36–3.54 (m,
8H, H-6000a, 6000b, 2000, 4000, 500, 600, and –CH2–), 2.89–3.04
(m, 2H, –CH2–), 2.21 (ddd, 1H, J¼13.0, 5.0, 5.0 Hz, Heq-
200), 1.73–1.79 (m, 2H, –CH2–), 1.21 (q, 1H, J¼12.0 Hz,
Hax-200); 13C NMR (125 MHz, CD3OD): d 172.2 (–CO),
166.1 (C-2), 152.6 (C-4), 144.2 (C-6), 103.1 (C-5), 95.7
(C-1000), 92.6 (C-10), 85.2 (C-40), 78.5 (C-30), 75.6 (C-20),
74.6 (C-400), 73.9 (C-4000), 73.6 (C-600), 73.1 (C-3000), 72.5
(C-500), 64.9 (C-5000), 60.7 (C-2000), 59.8 (C-100), 59.7 (C-300),
52.5 (C-6000), 38.4 (–CH2–), 33.4 (C-200), 30.9 (–CH2–).
HRESI-MS Calcd for C24H35N16O11 ([M+H]+): 723.2665,
found: 723.2670.
3.9.3. Compound 4c. Yield: 91% from 3a, white foam. 1H
NMR (500 MHz, CD3OD): d 7.76 (d, 1H, J¼1.0 Hz, H-6),
6.11 (t, 1H, J¼6.5 Hz, H-10), 5.14 (d, 1H, J¼4.0 Hz,
H-1000), 4.57–4.60 (m, 1H, H-30), 4.35 (d, 1H, J¼4.0 Hz,
H-40), 3.99–4.02 (m, 1H, H-5000), 3.77–3.93 (m, 3H, H-100,
3000, and 300), 3.64 (dd, 1H, J¼10.5, 3.5 Hz, H-6000a),
3.34–3.54 (m, 8H, H-400, 6000b, 2000, 4000, 500, 600, and –CH2–),
3.07–3.19 (m, 2H, –CH2–), 2.63–2.68 (m, 1H, H-20a),
2.30–2.34 (m, 1H, H-20b), 2.20 (ddd, 1H, J¼13.0, 4.5,
4.5 Hz, Heq-200), 1.89 (d, 3H, J¼1.5 Hz, 5-CH3), 1.21 (q,
1H, J¼12.5 Hz, Hax-200); 13C NMR (125 MHz, CD3OD):
d 172.4 (–CO), 166.3 (C-2), 152.4 (C-4), 139.8 (C-6),
111.8 (C-5), 96.0 (C-1000), 89.5 (C-10), 84.5 (C-40), 78.8
(C-400), 75.0 (C-4000), 73.6 (C-600), 73.3 (C-3000), 72.5 (C-500),
65.2 (C-30), 65.0 (C-5000), 60.7 (C-2000), 59.6 (C-100 and 300),
52.5 (C-6000), 50.6 (–CH2–), 40.5 (–CH2–), 36.7 (C-20),
33.4 (C-200), 12.5 (–CH3). HRESI-MS Calcd for
C24H34N19O9 ([M+H]+): 732.2781, found: 732.2753.
3.9.7. Compound 6b. Yield: 82% from 3c, white foam. 1H
NMR (500 MHz, CD3OD): d 8.10 (d, 1H, J¼8.0 Hz, H-6),
5.83 (d, 1H, J¼6.0 Hz, H-10), 5.74 (d, 1H, J¼8.0 Hz, H-5),
5.13 (d, 1H, J¼4.0 Hz, H-1000), 4.43 (dd, 1H, J¼6.0, 5.0 Hz,
H-20), 4.35 (d, 1H, J¼3.0 Hz, H-40), 4.22 (dd, 1H, J¼5.0,
3.5 Hz, H-30), 3.80–4.02 (m, 4H, H-5000, 3000, 100, and 300),
3.66 (dd, 1H, J¼10.0, 3.5 Hz, H-400), 3.27–3.54 (m, 8H, H-
6000a, 6000b, 2000, 4000, 500, 600, and –CH2–), 2.88–3.04 (m, 2H,
–CH2–), 2.24 (ddd, 1H, J¼13.0, 5.0, 5.0 Hz, Heq-200), 1.55–
1.67 (m, 4H, –CH2CH2–), 1.23 (q, 1H, J¼12.0 Hz, Hax-200);
13C NMR(100 MHz, CD3OD): d 170.8 (–CO), 164.7 (C-2),
151.2 (C-4), 142.9 (C-6), 101.6 (C-5), 94.4 (C-1000), 91.4
(C-10), 83.8 (C-40), 77.0 (C-30), 73.8 (C-20), 73.2 (C-400),
72.6 (C-4000), 72.2 (C-600), 71.8 (C-3000), 71.1 (C-500), 63.5
(C-5000), 59.3 (C-2000), 58.4 (C-100), 58.3 (C-300), 51.1 (C-6000),
50.3 (–CH2–), 38.8 (–CH2–), 31.9 (C-200), 26.9 (–CH2–),
26.7 (–CH2–). HRESI-MS Calcd for C25H37N16O11
([M+H]+): 737.2822, found: 737.2821.
3.9.4. Compound 4d. Yield: 91% from 3b, white foam. 1H
NMR (500 MHz, CD3OD): d 7.74 (d, 1H, J¼1.0 Hz, H-6),
6.15 (t, 1H, J¼6.5 Hz, H-10), 5.14 (d, 1H, J¼4.0 Hz,
H-1000), 4.59–4.62 (m, 1H, H-30), 4.34 (d, 1H, J¼4.0 Hz,
H-40), 3.99–4.02 (m, 1H, H-5000), 3.81–3.91 (m, 3H, H-100,
3000, and 300), 3.69 (dd, 1H, J¼10.0, 3.5 Hz, H-6000a),
3.34–3.55 (m, 8H, H-400, 6000b, 2000, 4000, 500, 600, and –CH2–),
2.96–3.12 (m, 2H, –CH2–), 2.59–2.64 (m, 1H, H-20a),
2.31–2.36 (m, 1H, H-20b), 2.22 (ddd, 1H, J¼13.0, 5.0,
5.0 Hz, Heq-200), 1.90 (d, 3H, J¼1.0 Hz, 5-CH3), 1.76–1.82