S. J. Keding et al. / Tetrahedron 59 (2003) 7023–7031
7029
26.32, 23.29, 21.89, 21.20, 20.96, 20.93, 20.88; MS
(LR-ESI) calculated for C57H69N5O21Na [MþNa]þ
1182.5, found 1182.5.
11.5 Hz), 4.52 (d, 1H, J¼11.9 Hz), 4.48 (d, 1H,
J¼11.4 Hz), 4.45 (d, 1H, J¼11.4 Hz), 4.43 (d, 1H,
J¼11.4 Hz), 4.37–4.25 (m, 7H), 4.21 (d, 1H, J¼10.5 Hz),
4.20–4.12 (m, 3H), 4.07 (d, 1H, J¼11.7 Hz), 4.02 (d, 1H,
J¼11.7 Hz), 3.97 (m, 1H), 3.95–3.84 (m, 4H), 3.76–3.60
(m, 4H), 3.52 (dd, 1H, J¼10.0, 7.7 Hz), 3.44 (d, 1H,
J¼9.0 Hz), 3.42 (d, 1H, J¼9.0 Hz), 3.35–3.24 (m, 3H),
3.24–3.17 (m, 2H), 3.12 (dd, 1H, J¼9.4, 4.8 Hz), 1.80 (s,
3H), 1.82–1.68 (m, 2H), 1.73 (d, 1H, J¼5.3 Hz), 1.67–1.50
(m, 2H), 1.30–1.18 (m, 2H); 13C NMR (CDCl3, 100 MHz)
d 172.78, 169.92, 156.40, 144.37, 144.23, 141.71, 139.82,
139.17, 139.01, 138.94, 138.74, 138.60, 138.51, 138.45,
135.74, 129.04, 128.88, 128.85, 128.70, 128.69, 128.67,
128.58, 128.42, 128.36, 128.33, 128.25, 128.13, 128.03,
127.97, 127.93, 127.88, 127.51, 125.61, 125.55, 120.38,
103.02, 101.35, 99.84, 81.77, 81.08, 79.70, 77.98, 77.67,
77.36, 77.32, 75.76, 75.66, 75.62, 74.76, 73.58, 73.52,
73.49, 73.45, 73.26, 72.87, 72.52, 70.48, 69.56, 69.12,
68.55, 68.22, 67.85, 67.59, 67.46, 54.41, 47.57, 32.53,
29.32, 22.11, 21.30; MS (LR-ESI) 1731 [MþNa]þ.
4.2.8. Compound 14. Obtained from 13 according to the
general procedures as white solid in 65% yield (0.219 g).
[a]2D4¼þ28.88 (c 1.01, CH3OH); 1H NMR (CD3OD,
400 MHz) d 7.78 (d, 2H, J¼7.5 Hz), 7.66 (t, 2H, J¼
7.0 Hz), 7.38 (t, 2H, J¼7.4 Hz), 7.30 (t, 2H, J¼7.4 Hz),
5.31–5.48 (m, 3H), 5.14 (dd, 1H, J¼11.5, 2.9 Hz), 4.77–
4.96 (m, 3H), 4.42 (dd, 1H, J¼11.6, 3.4 Hz), 4.35 (d, 1H,
J¼6.9 Hz), 4.05–4.40 (m, 7H), 3.99 (m, 1H), 3.65–3.93 (m,
2H), 3.78 (s, 3H), 3.45 (m, 1H), 3.34 (m, 1H), 2.58 (dd, 1H,
J¼12.7, 4.6 Hz), 2.15 (s, 3H), 2.11 (s, 3H), 2.09 (s, 3H),
1.99 (s, 3H), 1.95 (s, 3H), 1.93 (s, 6H), 1.83 (s, 3H), 1.35–
1.85 (m, 6H); 13C NMR (CD3OD, 100 MHz) d 177.04,
173.73, 173.57, 172.50, 172.34, 172.05, 171.92, 171.72,
171.55, 169.33, 158.55, 145.47, 145.32, 142.65, 128.91,
128.30, 126.38, 121.06, 100.00, 98.95, 73.39, 70.72, 69.97,
69.55, 69.36, 69.09, 68.84, 68.57, 67.93, 64.44, 63.51,
56.01, 53.58, 50.11, 39.01, 32.99, 30.04, 23.72, 22.85,
22.71, 21.37, 21.05, 20.92, 20.88, 20.84; MS (HR-FAB)
calculated for C53H67N3O24Na [MþNa]þ 1152.4012, found
1152.4007.
4.2.11. Compound 19. A mixture of acceptor 17 (49.0 mg,
0.029 mmol, 1 equiv.), donor 18 (73.8 mg, 0.058 mmol,
˚
2.0 equiv.), and freshly activated 4 A molecular sieves
(120 mg) was dissolved in CH2Cl2 (0.60 mL), and the
resultant slurry was stirred at room temperature for 30 min.
MeOTf (19.0 mL, 0.017 mmol, 6 equiv.) was added to the
mixture at 2208C and the reaction mixture was allowed to
warm to 08C. After 4 h, the reaction was quenched with
Et3N (50 mL), filtered through celite, and partitioned
between EtOAc and saturated NaHCO3 solution. Organic
phase was dried over MgSO4, filtered and concentrated.
Flash column chromatography (3:7 EtOAc/hexane) of the
residue gave the desired product (76.0 mg, 90%) as a white
foam: 1H NMR (CDCl3, 400 MHz): d 7.68 (d, 2H,
J¼7.5 Hz), 7.61 (d, 2H, J¼7.4 Hz), 7.52 (d, 2H,
J¼7.3 Hz), 7.35–6.92 (m, 67H), 5.28 (d, 1H, J¼8.3 Hz),
5.10 (d, 1H, J¼7.5 Hz), 5.07 (d, 1H, J¼7.5 Hz), 5.05–4.99
(m, 2H), 4.98 (d, 1H, J¼3.5 Hz), 4.93 (d, 1H, J¼11.5 Hz),
4.88 (d, 1H, J¼11.4 Hz), 4.84–4.73 (m, 6H), 4.73–4.4.49
(m, 2H), 4.69–4.65 (m, 3H), 4.64 (d, 1H, J¼7.4 Hz), 4.63–
4.53 (m, 5H), 4.50–4.37 (m, 5H), 4.36 (d, 1H, J¼4.5 Hz),
4.35–4.30 (m, 3H), 4.30–4.23 (m, 2H), 4.23 (d, 1H,
J¼11.5 Hz), 4.19 (d, 1H, J¼6.7 Hz), 4.13 (m, 1H), 4.12 (d,
1H, J¼11.8 Hz), 4.07 (d, 1H, J¼8.1 Hz), 4.07–3.96 (m,
6H), 3.95–3.92 (m, 2H), 3.92–3.75 (m, 3H), 3.74–3.65 (m,
6H), 3.65–3.56 (m, 6H), 3.53 (dd, 1H, J¼9.8, 8.6 Hz), 3.43
(dd, 1H, J¼8.6, 8.6 Hz), 3.36 (dd, 1H, J¼8.2, 8.2 Hz),
3.33–3.23 (m, 2H), 3.20–3.12 (m, 2H), 2.81 (dd, 1H,
J¼9.3, 1.9 Hz), 2.78 (s, 1H), 2.65 (m, 1H), 1.83–1.70 (m,
2H), 1.73 (s, 3H), 1.52–1.43 (m, 2H), 1.29–1.17 (m, 2H),
1.13 (d, 3H, J¼6.4 Hz), 1.15–0.80 (m, 42H); MS (LR-ESI)
2948 [MþNa]þ.
4.2.9. Compound 16. Obtained from 15 according to the
general procedure. Purification by flash column chromato-
graphy (3:7 EtOAc/hexane) of the residue provided a white
foam (0.341 g, 70% for two steps). 1H NMR (CDCl3,
400 MHz) d 7.68 (d, 2H, J¼7.5 Hz), 7.50 (d, 2H,
J¼7.3 Hz), 7.35–7.05 (m, 49H), 6.92 (d, 2H, J¼8.5 Hz),
6.68 (d, 2H, J¼8.5 Hz), 5.35 (d, 1H, J¼8.2 Hz), 5.12 (d, 1H,
J¼7.5 Hz), 5.08 (d, 1H, J¼7.5 Hz) 4.97 (d, 1H, J¼3.3 Hz),
4.94 (d, 1H, J¼11.8 Hz), 4.82–4.75 (m, 2H), 4.72 (d, 1H,
J¼4.6 Hz), 4.70 (d, 1H, J¼4.6 Hz), 4.69 (d, 1H, J¼
10.6 Hz), 4.67 (d, 1H, J¼15.1.Hz), 4.58 (d, 1H, J¼
15.1 Hz), 4.45–4.40 (m, 3H), 4.38 (d, 1H, J¼6.9 Hz),
4.37–4.20 (m, 7H), 4.20–4.09 (m, 3H), 4.09–3.98 (m, 3H),
3.98–3.90 (m, 3H), 3.88–3.80 (m, 2H), 3.79–3.70 (m, 2H),
3.69 (s, 3H), 3.61 (d, 1H, J¼7.3 Hz), 3.57 (dd, 2H, J¼7.0,
6.5 Hz), 3.46–3.25 (m, 6H), 3.25–3.18 (m, 2H), 3.10 (dd,
1H, J¼7.2, 3.6 Hz), 2.30 (s, 1H), 1.85–1.70 (m, 2H), 1.72–
1.55 (m, 2H), 1.40–1.25 (m, 2H); 13C NMR (CDCl3,
100 MHz) d 172.85, 159.27, 156.43, 144.37, 144.24,
141.71, 139.50, 139.38, 139.14, 139.10, 139.01, 138.74,
138.48, 135.75, 131.26, 129.18, 129.04, 128.91, 128.80,
128.70, 128.67, 128.54, 128.48, 128.26, 128.16, 128.11,
127.93, 127.52, 125.58, 120.38, 114.09, 113.97, 103.17,
103.01, 100.98, 82.51, 81.88, 79.80, 77.68, 77.08, 77.01,
75.77, 75.65, 75.30, 74.99, 74.81, 74.30, 73.68, 73.61,
73.50, 73.45, 72.70, 72.48, 69.83, 69.55, 68.68, 68.33,
68.10, 67.54, 67.44, 55.65, 54.35, 47.58, 32.45, 29.23,
22.21; MS (LR-ESI) 1809 [MþNa]þ.
4.2.10. Compound 17. Obtained from 16 according to the
general procedures in 90% yield (0.296 g). 1H NMR
(CDCl3, 400 MHz) d 7.68 (d, 2H, J¼7.4 Hz), 7.52 (d, 2H,
J¼7.3 Hz), 7.35–7.03 (m, 49H), 5.29 (d, 1H, J¼7.8 Hz),
5.12 (d, 1H, J¼12.3 Hz), 5.08 (d, 1H, J¼12.3 Hz), 5.00 (d,
1H, J¼3.3 Hz), 4.87 (d, 1H, J¼11.4 Hz), 4.85 (d, 1H,
J¼7.5 Hz), 4.83 (d, 1H, J¼8.0 Hz), 4.77 (d, 1H, J¼
11.3 Hz), 4.72 (d, 1H, J¼12.4 Hz), 4.69 (d, 1H, J¼
11.1 Hz), 4.62 (d, 1H, J¼11.4 Hz), 4.53 (d, 1H, J¼
4.2.12. Compound 22. Obtained from 21 according to the
general procedures in 57% yield (5.4 mg) 1H NMR (CDCl3,
400 MHz): d 7.72 (d, 2H, J¼7.4 Hz), 7.52 (d, 2H,
J¼7.3 Hz), 7.40–7.18 (m, 14H), 6.62 (d, 1H, J¼6.6 Hz),
5.52 (d, 1H, J¼3.0 Hz), 5.39 (d, 1H, J¼3.5 Hz), 5.36 (d, 1H,
J¼8.5 Hz), 5.33 (d, 1H, J¼3.1 Hz), 5.22 (dd, 1H, J¼10.9,
3.0 Hz), 5.20–5.05 (m, 6H), 4.99–4.85 (m, 4H), 4.68 (dd,
1H, J¼10.9, 2.3 Hz), 4.50–4.20 (m, 11H), 4.20–3.95 (m,
10H), 3.94–3.87 (m, 3H), 3.85–3.73 (m, 3H), 3.67 (m, 1H),