C. M. Huwe et al. / Bioorg. Med. Chem. 7 (1999) 773±788
785
8.2 Hz), 4.91 (dd, 0.87H, J=3.7, 8.3 Hz), 5.04 (d, 1H,
J=12.3 Hz), 5.07 (d, 1H, J=12.3 Hz), 6.07 (dt, 1H,
J=6.3, 15.9 Hz), 6.48 (d, 1H, J=15.9 Hz), 6.76±6.82 (m,
2H), 7.20±7.35 (m, 29H); 13C NMR (100 MHz, CDCl3):
d 14.06, 15.56, 29.29, 29.62, 30.68, 54.82, 55.17, 55.28,
61.71, 66.48, 68.32, 71.37, 71.45, 72.87, 73.15, 73.32,
75.23, 75.85, 76.49, 113.80, 123.28, 127.30, 127.39,
127.51, 127.69, 127.74, 127.97, 128.15, 128.17, 128.25,
128.38, 128.47, 129.27, 132.45, 135.64, 137.53, 138.15,
138.43, 138.63, 159.20, 169.68, 170.05, 171.64, 172.59.
HRMS (FAB): C65H74N2O14Cs (M+Cs), calcd
1239.4194, found 1239.4142.
138.12, 138.38, 138.57, 169.71, 169.98, 171.66, 172.58.
HRMS (FAB): C68H74N2O13Cs (M+Cs), calcd
1295.4245, found 1259.4189.
Compound 31f. Prepared according to general procedure
D using 96 mg vinyl¯uoren and EtOAc/hexanes (1/1 to
1
3/2) to give 31f (204 mg, 70%). H NMR (400 MHz,
CDCl3): d 1.18±1.24 (m, 6H), 1.76 (m, 2H), 2.36±2.43
(m, 2H), 2.57 (dt, 1H, J=6.2, 17.4 Hz), 2.67 (dt, 1H,
J=7.0, 17.4 Hz), 3.58 (dd, 1H, J=4.9, 9.8 Hz), 3.63±
3.70 (m, 3H), 3.82 (s, 2H), 3.76±3.86 (m, 3H), 3.97
(broad m, 1H), 4.03 (broad m, 1H), 4.42±4.50 (m, 3H),
4.28±4.35 (m, 2H), 4.44 (d, 1H, J=11.8 Hz), 4.47 (d,
1H, J=11.8 Hz), 4.50 (d, 1H, J=11.9 Hz), 4.53 (d, 1H,
J=11.8 Hz), 4.56 (d, 1H, J=11.9 Hz), 4.61 (s, 2H), 4.64
(dd, 1H, J=4.8, 6.9 Hz), 4.74 (d, 1H, J=11.8 Hz), 4.94
(dd, 1H, J=3.5, 8.2 Hz), 5.02 (d, 1H, J=12.7 Hz), 5.05
(d, 1H, J=12.7 Hz), 6.25 (dt, 1H, J=6.1, 15.8 Hz), 6.62
(d, 1H, J=15.8 Hz), 6.90 (d, 1H, J=7.1 Hz), 7.18±7.40
(m, 29H), 7.50 (m, 2H), 7.65 (d, 1H, J=7.9 Hz), 7.71 (d,
1H, J=7.5 Hz). 13C NMR (100 MHz, CDCl3): d 14.07,
15.64, 29.27, 29.61, 30.65, 36.69, 54.83, 55.34, 61.71,
66.45, 68.24, 71.30, 71.38, 71.43, 72.84, 72.88, 73.23,
73.30, 75.29, 75.90, 76.43, 119.79, 122.87, 124.94,
124.99, 125.64, 126.61, 126.68, 127.27, 127.38, 127.51,
127.66, 127.71, 127.94, 127.99, 128.11, 128.15, 128.24,
128.36, 128.44, 133.07, 135.18, 135.61, 137.52, 138.16,
138.41, 138.61, 141.30, 143.40, 143.49, 169.69, 170.03,
171.66, 172.59. HRMS (FAB): C71H76N2O13Cs
(M+Cs), calcd 1297.4402, found 1297.4445.
Compound 31d. Prepared according to General Proce-
dure D using 78 mg penta¯uorostyrene and EtOAc/
toluene (1/2) to give 31d (50 mg, 17%). Mixture of ste-
reoisomers in a 0.7/0.3 ratio. 1H NMR (400 MHz,
CDCl3): d 1.20 (t, 3H, J=7.0 Hz), 1.23 (d, 3H,
J=6.8 Hz), 1.69±1.79 (m, 2H), 2.36±2.49 (m, 2H), 2.53±
2.73 (m, 2H), 3.58 (m, 1H), 3.62±3.70 (m, 4H), 3.80
(broad m, 2H), 3.94 (m, 1H), 4.00 (m, 1H), 4.10±4.19
(m, 3H), 4.24±4.35 (m, 2H), 4.43±4.57 (m, 5H), 4.61 (s,
2H), 4.62 (m, 1H), 4.73 (d, 1H, J=11.8), 4.90 (dd, 0.3H,
J=3.7, 7.4), 4.92 (dd, 0.7H, J=3.7, 8.2), 5.06 (d, 1H,
J=12.4), 5.07 (d, 1H, J=12.4), 6.20 (dt, 0.7H, J=6.2,
15.9), 6.50 (m, 0.6H), 6.54 (d, 0.7H, J=15.9), 6.78 (d,
0.7H, J=7.5), 6.80 (d, 0.3H, J=8.6), 7.18±7.38 (m,
26H). 13C NMR (100 MHz, CDCl3): d 14.09, 15.58,
29.32, 29.66, 30.71, 54.82, 54.89, 55.22, 55.28, 54.82,
54.88, 55.22, 55.28, 61.78, 61.86, 66.53, 68.35, 71.03,
71.28, 71.42, 71.48, 72.93, 73.21, 73.37, 75.42, 75.87,
76.38, 76.51, 125.61, 126.51, 127.33, 127.44, 127.56,
127.65, 127.72, 127.79, 128.01, 128.16, 128.21, 128.30,
128.42, 128.48, 128.50, 132.69, 135.65, 136.52, 137.40,
137.53, 138.10, 138.16, 138.41, 138.44, 138.64, 169.72,
169.81, 170.05, 171.68, 171.75, 172.63. HRMS (FAB):
C64H67F5N2O13Cs (M+Cs), calcd 1299.3618, found
1299.3540.
Compound 31g. Prepared according to General Proce-
dure D using 90 mg 4-vinylbiphenyl and EtOAc/toluene
1
(1/2) to give 31g (209 mg, 73%). H NMR (400 MHz,
CDCl3): d 1.20 (t, 3H, J=7.1 Hz), 1.22 (d, 3H,
J=6.5 Hz), 1.72±1.77 (m, 2H), 2.39 (m, 2H), 2.58 (dt,
1H, J=6.4, 17.4 Hz), 2.68 (dt, 1H, J=6.8, 17.4 Hz), 3.58
(dd, 1H, J=5.1, 10.0 Hz), 3.63±3.71 (m, 4H), 3.76±3.85
(broad m, 2H), 3.96 (m, 1H), 4.02 (m, 1H), 4.11±4.19
(m, 3H), 4.27±4.34 (m, 2H), 4.44 (d, 1H, J=12.1 Hz),
4.49 (d, 1H, J=11.8 Hz), 4.51 (d, 1H, J=11.9 Hz), 4.56
(d, 1H, J=12.1 Hz), 4.57 (d, 1H, J=11.9 Hz), 4.61 (s,
2H), 4.64 (dd, 1H, J=4.8, 7.3 Hz), 4.73 (d, 1H,
J=11.8 Hz), 4.94 (dd, 1H, J=3.7, 8.3 Hz), 5.03 (d, 1H,
J=12.5 Hz), 5.06 (d, 1H, J=12.5 Hz), 6.25 (dt, 1H,
J=6.1, 15.9 Hz), 6.58 (d, 1H, J=15.9 Hz), 6.82 (d, 1H,
J= 7.4 Hz), 7.21±7.33 (m, 26H), 7.36±7.42 (m, 5H), 7.50
(brd, 2H, J=8.3 Hz), 7.56 (brd, 2H, J=7.1 Hz). 13C
NMR (100 MHz, CDCl3): d 14.09, 15.61, 29.30, 30.69,
54.82, 55.30, 61.76, 66.49, 68.34, 71.29, 71.36, 71.47,
72.90, 73.19, 73.35, 75.45, 75.86, 76.50, 125.74, 126.85,
126.93, 127.13, 127.23, 127.31, 127.41, 127.54, 127.69,
127.76, 127.99, 128.16, 128.19, 128.27, 128.40, 128.48,
128.71, 132.17, 135.57, 135.63, 137.52, 138.16, 138.43,
138.63, 140.31, 140.58, 169.71, 170.02, 171.68, 172.61.
HRMS (FAB): C70H76N2O13Cs (M+Cs), calcd
1285.4402, found 1285.4459.
Compound 31e. Prepared according to General Proce-
dure D using 85 mg 2-vinylnaphtalene and EtOAc/
toluene 1/2 to give 31e (106 mg, 71%). 1H NMR
(400 MHz, CDCl3): d 1.19 (t, 3H, J=7.0 Hz), 1.23 (d,
3H, J=6.5 Hz), 1.73±1.80 (m, 2H), 2.32±2.43 (m, 2H),
2.56 (dt, 1H, J=6.1, 17.4 Hz), 2.66 (dt, 1H, J=6.9,
17.4 Hz), 3.58 (dd, 1H, J=5.1, 9.9 Hz), 3.63±3.70 (m,
3H), 3.75±3.87 (m, 3H), 3.96±4.05 (m, 2H), 4.08±4.23
(m, 3H), 4.31±4.34 (m, 2H), 4.44 (d, 1H, J=11.8 Hz),
4.46 (d, 1H, J=11.8 Hz), 4.49 (d, 1H, J=12.7 Hz), 4.52
(d, 1H, J=12.7 Hz), 4.56 (d, 1H, J=11.7 Hz), 4.61 (s,
2H), 4.66 (dd, 1H, J=5.0, 7.0 Hz), 4.73 (d, 1H,
J=11.7 Hz), 4.96 (dd, 1H, J=3.4, 8.1 Hz), 5.02 (d, 1H,
J=12.4 Hz), 5.05 (d, 1H, J=12.4 Hz), 6.34 (dt, 1H,
J=6.0, 15.8 Hz), 6.71 (d, 1H, J=15.8 Hz), 6.88 (d, 1H,
J=7.2 Hz), 7.13±7.32 (m, 25H), 7.38±7.43 (m, 3H), 7.54
(brd, 1H, J=8.5 Hz), 7.66±7.76 (m, 4H). 13C NMR
(100 MHz, CDCl3): d 14.03, 15.59, 21.35, 28.81, 29.23,
29.57, 30.60, 54.80, 55.27, 61.69, 66.42, 68.27, 71.24,
71.28, 71.39, 72.82, 72.86, 73.16, 73.28, 75.42, 75.84,
76.44, 123.51, 125.18, 125.76, 126.01, 126.09, 126.47,
127.25, 127.36, 127.48, 127.52, 127.64, 127.69, 127.91,
127.94, 128.06, 128.09, 128.13, 128.22, 128.33, 128.41,
128.91, 132.63, 132.91, 133.40, 133.96, 135.58, 137.49,
Compound 31i. Byproduct in the preparation of 31d.
117 mg (47%); EtOAc/hexanes (1/1 to 2/1) mixture of
1
stereoisomers in a 0.75/0.25 ratio. H NMR (400 MHz,
CDCl3): d 1.15±1.24 (m, 12H), 1.66±1.75 (m, 4H), 2.37±
2.58 (m, 6H), 2.66 (m, 2H), 3.55±3.68 (m, 8H), 3.76±3.87