10924
L. L. Etchells et al. / Tetrahedron 62 (2006) 10914–10927
(C(9)H2 to C(22)H2, C(26)H2 to C(39)H2 and C(42)H2,
many overlapping), 43.7 (C(8)H2), 45.0 (C(41)H2), 52.6
(C(4)H), 52.8 (CO2CH3), 65.5 (C(5)H), 76.3 (C(3)H), 90.4
(C(6)H), 111.7, 112.3, 118.5, 120.0, 122.5, 122.7, 127.3,
136.6 (C(43), C(44)H, C(46), C(47)H to C(50)H and
C(51)), 166.2 (C(2)), 173.2 (C(24)O), 200.0 (C(7)O); m/z
(+ve ion electrospray) 785 ([M+Na]+, 100%); found
785.6165, C49H82N2O4Na ([M+Na]+) requires 785.6167.
556 ([M+Na]+, 100%); found 556.3405, C34H47NO4Na
([M+Na]+) requires 556.3397.
4.7.9. Data for (3R*,4S*,5S*)-1-(2-(1H-indol-3-yl)-ethyl)-
2-(20-oxo-tetradec-E-ylidene)-3-hydroxy-5-phenyl-pyr-
rolidine-4-carboxylic acid methyl ester (50). Ayellow oil;
Rf 0.47 (petroleum ether:ethyl acetate, 3:1); nmax (film)/
cmꢀ1 3326br (O–H), 2924s and 2852m (C–H), 1738s
(C]O, ester), 1618w (C]O, vinylogous amide), 1525s,
1457m, 1437w, 1250w; dH (300 MHz, CDCl3) 0.94 (3H, t,
J 6.6, C(19)H3), 1.25–1.40 (18H, m, C(10)H2 to C(18)H2),
1.62–1.70 (2H, m, C(9)H2), 2.38 (2H, t, J 7.6, C(8)H2),
2.82–2.93 (1H, m, one of C(29)H2), 3.05–3.24 (2H, m, one
of C(28)H2 and one of C(29)H2), 3.24 (1H, wt, J 7.2,
C(4)H), 3.45–3.58 (1H, m, one of C(28)H2), 3.72 (3H, s,
CO2CH3), 4.63 (1H, d, J 7.2, C(5)H), 5.25 (1H, s, C(6)H),
5.35 (1H, d, J 6.3, C(3)H), 7.00 (1H, d, J 2.1, C(31)H),
7.10–7.43 (10H, m, C(23)H to C(27)H, C(34)H to C(37)H
and OH), 8.35 (1H, br s, NH); dC (75 MHz, CDCl3) 14.4
(C(19)H3), 21.6 (C(29)H2), 23.0, 26.6, 29.7, 29.9, 29.96,
29.99, 32.2 (C(9)H2 to C(18)H2, some overlapping), 43.8
(C(8)H2), 45.5 (C(28)H2), 52.8 (CO2CH3), 57.0 (C(4)H),
69.5 (C(5)H), 76.1 (C(3)H), 90.9 (C(6)H), 111.7, 112.1,
118.5, 119.8, 122.6, 127.3, 128.2, 129.3, 129.4 (C(23)H
and C(27)H, C(24)H and C(26)H, C(25)H, C(34)H,
C(35)H, C(36)H, C(37)H and 2ꢂquaternary C), 136.6,
138.4 (2ꢂquaternary C), 166.3 (C(2)), 172.3 (C(20)O),
200.6 (C(7)O); m/z (+ve ion electrospray) 595 ([M+Na]+,
20%), 573 ([M+H]+, 70), 295 (25); found 573.3689,
C36H49N2O4 ([M+H]+) requires 573.3687.
4.7.7. Data for (3R*,4S*,5S*)-1-phenethyl-2-(20-oxo-octa-
dec-E-ylidene)-3-hydroxy-5-ethylpyrrolidine-4-carbox-
ylic acid isopropyl ester (48). A pale yellow oil; Rf 0.16
(petroleum ether:ethyl acetate, 9:1); nmax (film)/cmꢀ1
3222br (O–H), 2924s and 2853s (C–H), 1732s (C]O,
ester), 1625m (C]O, vinylogous amide), 1535s, 1466s,
1249m, 1180m, 1107s; dH (300 MHz, CDCl3) 0.79–0.84
(6H, m, C(23)H3 and C(26)H3), 1.10–1.28 (32H, m,
C(10)H2 to C(22)H2 and OCH(CH3)2), 1.48–1.57 (3H, m,
C(9)H2 and one of C(25)H2), 1.72–1.80 (1H, m, one of
C(25)H2), 2.29 (2H, td, J 7.5, 3.2, C(8)H2), 2.72–2.78 (1H,
m, one of C(28)H2), 2.77 (1H,wt, J 6.0, C(4)H), 2.84 (1H,
ddd, J 14.4, 9.0, 4.5, one of C(28)H2), 3.25 (1H, ddd,
J 14.4, 9.0, 4.5, one of C(27)H2), 3.40 (1H, ddd, J 14.4,
9.0, 4.5, one of C(27)H2), 3.58–3.62 (1H, m, C(5)H), 4.98
(1H, septet, J 6.2, CO2CH(CH3)2), 5.03 (1H, br s, C(6)H),
5.13 (1H, d, J 6.0, C(3)H), 6.88 (1H, br s, OH), 7.12 (2H,
d, J 7.0, C(30)H and C(34)H), 7.17–7.20 (1H, m, C(32)H),
7.26 (2H, d, J 7.0, C(31)H and C(33)H); dC (75 MHz,
CDCl3) 8.7, 14.4 (C(23)H3 and C(26)H3), 21.9, 22.0, 23.0,
25.9, 26.5, 29.4, 29.82, 29.85, 29.9, 30.0, 32.2, 32.3 (C(9)H2
to C(22)H2, OCH(CH3)2, C(25)H2 and C(28)H2, many over-
lapping), 43.7 (C(8)H2), 46.1 (C(27)H2), 52.4 (C(4)H), 66.7
(C(5)H), 69.3 (CO2CH(CH3)2), 76.0 (C(3)H), 90.5 (C(6)H),
127.2 (C(32)H), 128.9 (C(30)H and C(34)H), 129.1 (C(31)H
and C(33)H), 138.3 (C(29)), 166.3 (C(2)), 172.1 (C(24)O),
200.0 (C(7)O); m/z (+ve ion electrospray) 592 ([M+Na]+,
13%), 570 ([M+H]+, 100); found 570.4509, C36H60NO4
([M+H]+) requires 570.4517.
4.7.10. Data for (3R*,4S*,5S*)-1-phenethyl-2-(20-oxo-tet-
radec-E-ylidene)-3-hydroxy-5-ethylpyrrolidine-4-car-
boxylic acid methyl ester (51). A yellow oil; Rf 0.47
(petroleum ether:ethyl acetate, 3:1); nmax (film)/cmꢀ1
2924s and 2853s (C–H), 1740s (C]O, ester), 1624m
(C]O, vinylogous amide), 1535s, 1463m, 1248w; dH
(300 MHz, CDCl3) 0.93 (3H, t, J 6.9, C(19)H3 or
C(23)H3), 0.94 (3H, t, J 7.5, C(19)H3 or C(23)H3), 1.26–
1.37 (18H, m, C(10)H2 to C(18)H2), 1.61–1.71 (3H, m,
C(9)H2 and one of C(22)H2), 1.82–1.93 (1H, m, one of
C(22)H2), 2.39–2.45 (2H, m, C(8)H2), 2.87 (1H, ddd, J
14.8, 9.0, 5.8, one of C(25)H2), 2.93–3.02 (1H, m, one of
C(25)H2), 2.96 (1H, wt, J 6.0, C(4)H), 3.37 (1H, ddd, J
14.8, 9.0, 5.8, one of C(24)H2), 3.53 (1H, ddd, J 14.8, 9.0,
5.8, one of C(24)H2), 3.74–3.82 (1H, m, C(5)H), 3.80 (3H,
s, CO2CH3), 5.16 (1H, s, C(6)H), 5.26 (1H, d, J 6.0,
C(3)H), 7.23–7.42 (5H, m, C(27)H to C(31)H); dC
(75 MHz, CDCl3) 8.6, 14.4 (C(19)H3 and C(23)H3), 23.0,
25.7, 26.6, 29.4, 29.8, 29.9, 30.0, 32.2, 32.3 (C(9)H2 to
C(18)H2, C(22)H2 and C(25)H2, some overlapping), 43.8
(C(8)H2), 46.1 (C(24)H2), 51.9 (C(4)H), 52.8 (CO2CH3),
66.3 (C(5)H), 76.0 (C(3)H), 90.6 (C(6)H), 127.2 (C(29)H),
128.9 (either C(27)H and C(31)H or C(28)H and C(30)H),
129.1 (either C(27)H and C(31)H or C(28)H and C(30)H),
138.2 (C(26)), 166.1 (C(2)), 173.0 (C(20)O), 200.1
(C(7)O); m/z (+ve ion electrospray) 508 ([M+Na]+, 90%),
486 ([M+H]+, 100), 417, (10), 212 (38); found 486.3574,
C30H48NO4 ([M+H]+) requires 486.3578.
4.7.8. Data for (3R*,4S*,5S*)-1-phenethyl-2-(20-oxo-tet-
radec-E-ylidene)-3-hydroxy-5-phenylpyrrolidine-4-car-
boxylic acid methyl ester (49). A pale yellow oil; Rf 0.19
(petroleum ether:ethyl acetate, 5:1); nmax (film)/cmꢀ1
3255br (O–H), 2924s and 2852s (C–H), 1739s (C]O,
ester), 1625m (C]O, vinylogous amide), 1533s, 1457m,
1251m; dH (300 MHz, CDCl3) 0.92 (3H, t, J 6.6,
C(19)H3), 1.24–1.41 (18H, m, C(10)H2 to C(18)H2), 1.64–
1.73 (2H, m, C(9)H2), 2.43–2.48 (2H, m, C(8)H2), 2.67
(1H, ddd, J 13.8, 8.7, 5.0, one of C(29)H2), 2.86–2.96 (1H,
m, one of C(29)H2), 3.00–3.13 (1H, m, one of C(28)H2),
3.23 (1H,wt, J 6.9, C(4)H), 3.41 (1H, ddd, J 13.8, 8.7, 5.0,
one of C(28)H2), 3.74 (3H, s, CO2CH3), 4.59 (1H, d, J 6.9,
C(5)H), 5.25 (1H, s, C(6)H), 5.33 (1H, d, J 6.9, C(3)H),
7.05–7.08 (2H, m, 2ꢂaromatic CH), 7.25–7.43 (8H, m,
8ꢂaromatic CH); dC (75 MHz, CDCl3) 14.4 (C(19)H3),
23.0, 26.6, 29.6, 29.8, 29.9, 30.0, 31.7, 32.2 (C(9)H2 to
C(18)H2 and C(29)H2, some overlapping), 43.9 (C(8)H2),
46.5 (C(28)H2), 52.8 (CO2CH3), 56.9 (C(4)H), 69.6
(C(5)H), 76.0 (C(3)H), 91.0 (C(6)H), 127.1, 128.1, 128.9,
129.1, 129.4 (C(23)H and C(27)H, C(24)H and C(26)H,
C(25)H, C(31)H and C(35)H, C(32)H and C(34)H and
C(33)H), 138.2, 138.5 (C(22) and C(30)), 165.9 (C(2)),
172.1 (C(20)O), 200.5 (C(7)O); m/z (+ve ion electrospray)
4.7.11. Data for (3R*,4S*,5S*)-1-benzyl-2-(20-oxo-tetra-
dec-E-ylidene)-3-hydroxy-5-phenylpyrrolidine-4-car-
boxylic acid methyl ester (52). A pale yellow oil