S. Su et al. / Tetrahedron 59 (2003) 8931–8946
8941
129.3, 129.1, 128.3, 126.9, 124.4, 124.3, 123.5, 121.3,
119.3, 115.2, 114.9, 101.5, 63.7, 53.8, 31.5, 31.1, 29.6, 26.3,
2.6, 25.5, 22.9, 21.4, 19.5, 18.6, 17.9, 16.9; IR (thin film)
(d, 1H, J¼7.6 Hz), 7.24 (d, 1H, J¼7.6 Hz), 7.04–6.91 (m,
2H), 6.76 (t, 1H, J¼10.4 Hz), 5.79 (d, 1H, J¼9.2 Hz), 5.31
(m, 1H), 4.53–4.47 (m, 2H), 3.07 (s, 3H), 2.18 (m, 1H), 1.85
(m, 1H), 1.74 (s, 3H), 1.66 (s, 3H), 1.63 (s, 3H), 0.90–0.54
(m, 12H); 13C NMR (75.0 MHz, DMSO-d6) d 173.2, 169.9,
168.0, 137.3, 136.0, 133.0, 127.3, 121.3, 121.0, 119.3,
118.7, 111.2, 105.5, 104.5, 62.2, 55.1, 52.9, 31.1, 30.1, 26.4,
25.9, 22.2, 19.4, 19.3, 19.0, 18.0, 17.8; IR (thin film) nmax
3312, 2966, 2929, 2874, 1739, 1653, 1542, 1496, 1373,
1244 cm21; CIHRMS [MþH]þ calculated for C28H41N4O3:
481.3180, found: 481.3207; [a]2D3¼þ45.68 (c¼0.5, CHCl3).
n
max 3407, 3319, 2966, 2929, 2874, 1693, 1640, 1493, 1452,
1493, 1452, 1370, 1712, 1091, 910, 732 cm21; CIHRMS
[MþH]þ calculated for C35H47N4O5S: 635.3269, found:
635.3286; [a]2D3¼þ74.08 (c¼0.10, CH2Cl2).
4.1.11. (12S,15S)-Terpeptin (2). 100 mg (4.17 mmol) of
Mg powder was mixed with 1 mL MeOH. The reaction
mixture was sonicated until evolution of H2 was observed
and then cooled to 08C. 24-Z (20 mg, 0.032 mmol) in 1 mL
MeOH was added. After the mixture was stirred for 2 h at
08C, 2 mL sat. NH4Cl was added and the reaction mixture
was extracted with EtOAc. The combined organic layers
were washed with brine, dried over Na2SO4, filtered, and
concentrated in vacuo. Purification on silica gel (3% Et3N,
50% EtOAc in CH2Cl2) provided 14.4 mg (0.030 mmol,
4.1.14. (12S,15R)-E-Terpeptin (30). Prepared from the
(12S,15R) stereoisomer of 24-E following the procedures
1
reported for 2. H NMR (400 MHz, CDCl3) d 8.14 (d, 1H,
J¼10.4 Hz), 8.03 (s, 1H), 7.75–7.73 (m, 1H), 7.38 (d, 1H,
J¼6.4 Hz), 7.27–7.23 (m, 1H), 7.12–7.06 (m, 2H), 6.39 (d,
1H, J¼14.8 Hz), 6.29 (d, 1H, J¼8 Hz), 5.31 (m, 1H), 4.82
(dd, 1H, J¼6.8 Hz), 4.60 (d, 1H, J¼10.8 Hz), 3.48 (d, 2H,
J¼7.2 Hz), 3.10 (s, 3H), 2.44–2.35 (m, 1H), 2.00 (s, 3H),
1.76 (s, 3H), 1.71 (s, 3H), 1.04–0.85 (m, 12H); 13C NMR
(75.0 MHz, CDCl3) d 174.1, 170.4, 166.2, 135.8, 135.6,
135.4, 128.0, 127.9, 127.3, 126.5, 121.5, 120.1, 119.60
119.56, 110.5, 107.6, 107.0, 63.3, 54.4, 31.3, 31.1, 29.6,
25.9, 25.6, 25.3, 23.1, 19.9, 19.5, 18.7, 17.8, 17.3; IR (thin
film) nmax 3293, 2966, 2930, 2874, 1652, 1553, 1460, 1373,
1314, 1221, 1094 cm21; CIHRMS [MþH]þ calculated for
C28H41N4O3: 481.3180, found: 481.3144; [a]2D3¼þ87.68
(c¼1.0, CHCl3).
1
95%) of 2 as a pale yellow solid. H NMR (400 MHz,
DMSO-d6) d 10.92 (s, 1H), 8.83 (d, 1H, J¼10.4 Hz), 8.05
(d, 1H, J¼8 Hz), 7.30 (d, 1H, J¼8 Hz), 7.23 (d, 1H, J¼
7.6 Hz), 7.03 (t, 1H, J¼7.2 Hz), 6.94 (m, 1H), 6.77 (t, 1H,
J¼9.6 Hz), 5.78(d, 1H, J¼9.2 Hz), 5.30 (m, 1H), 4.74 (d,
1H, J¼10.8 Hz), 4.41 (t, 1H, J¼8.4 Hz), 3.05 (s, 3H), 2.13
(m, 1H), 1.85 (m, 1H), 1.77 (s, 3H), 1.67 (s, 3H), 1.64 (s,
3H), 0.85–0.65 (m, 12H); 13C NMR (75.0 MHz, DMSO-d6)
d 173.0, 169.3, 168.0, 136.9,135.8, 132.6, 127.2, 121.1,
120.9, 120.6, 118.9, 118.6, 111.0, 105.4, 104.3, 60.6, 55.0,
54.1, 30.5, 30.0, 26.2, 25.7, 25.5, 22.1, 19.0, 18.6, 18.5,
18.4, 17.7; IR (thin film) nmax 3300, 2963, 2927, 1657, 1626,
1546, 1493, 1460 cm21; CIHRMS [MþH]þ calculated
for C28H41N4O3: 481.3180, found: 481.3178; [a]2D3¼
239.98 (c¼0.43, distilled CHCl3); [a]2D3¼242.98 (c¼0.77,
distilled MeOH); natural [a]2D3¼2135.28 (c¼0.1, distilled
CHCl3).
4.1.15. (12R,15S)-Z-Terpeptin (31). Prepared from the
(12R,15S) stereoisomer of 24-Z following the procedures
1
reported for 2. H NMR (400 MHz, DMSO-d6) d 10.96 (s,
1H), 8.63 (d, 1H, J¼10.4 Hz), 7.92 (d, 1H, J¼7.2 Hz), 7.30
(d, 1H, J¼7.6 Hz), 7.24 (d, 1H, J¼7.6 Hz), 7.04–6.91 (m,
2H), 6.76 (t, 1H, J¼10.4 Hz), 5.79 (d, 1H, J¼9.2 Hz), 5.30
(m, 1H), 4.53–4.47 (m, 2H), 3.07 (s, 3H), 2.18 (m, 1H),
2.02–2.15 (m, 1H), 1.87–1.82 (m, 1H), 1.74 (s, 3H), 1.66
(s, 3H), 1.63 (s, 3H), 0.90–0.54 (m, 12H); 13C NMR
(75.0 MHz, DMSO-d6) d 173.0, 169.4, 168.0, 137.1, 135.9,
132.7, 127.2, 122.1, 121.3, 120.74, 120.70, 119.0, 118.6,
111.0, 105.3, 104.1, 63.4, 61.9, 54.3, 52.9, 31.0, 30.0, 26.3,
25.7, 25.5, 22.3, 22.1, 19.23, 19.16, 18.9, 18.7, 17.9, 17.7;
IR (thin film) nmax 3310, 2966, 2929, 1653, 1635, 1541,
1496, 1458, 1093 cm21; CIHRMS [MþH]þ calculated for
C28H41N4O3: 481.3180, found: 481.3172; [a]2D3¼242.68
(c¼0.52, CHCl3).
4.1.12. (12S,15S)-E-Terpeptin (25). Prepared from 24-E
following the same procedure reported for 2. 1H NMR
(400 MHz, CDCl3) (1:1 mixture of rotamers) d 9.14 (d,
0.5H, J¼10 Hz), 7.98–7.95 (m, 1.5H), 7.75–7.71 (m, 1H),
7.38 (dd, 1H, J¼10.8, 14.8 Hz), 7.26–7.24 (m, 1H), 7.13–
7.06 (m, 2H), 6.71 (d, 0.5H, J¼9.6 Hz), 6.50 (d, 0.41H,
J¼14.8 Hz), 6.31 (d, 0.52H, J¼14.8 Hz), 6.19 (d, 0.5H, J¼
8.8 Hz), 5.31–5.27 (m, 1H), 4.86–4.79 (m, 1H), 4.63 (d,
0.5H, J¼7.2 Hz), 4.19 (d, 0.5H, J¼10.8 Hz), 3.50–3.46 (m,
2H), 3.12 (s, 1.5H), 2.97 (s, 1.5H), 2.57–2.48 (m, 0.5H),
2.42–2.33 (m, 0.5H), 2.07 (s, 1H), 2.00 (s, 2H), 1.77 (s, 3H),
1.72 (s, 3H), 1.03–0.83 (m, 12H); 13C NMR (75.0 MHz,
CDCl3) d 174.0, 172.3, 171.9, 170.1, 168.1, 166.4, 165.0,
135.9, 135.3, 126.5, 121.7, 121.6, 120.2, 120.1, 119.9,
119.6, 119.57, 119.5, 119.4, 110.6, 110.5, 107.5, 107.3,
107.0, 66.7, 63.0, 60.4, 53.9, 53.8, 31.5, 31.1, 30.7, 29.6,
29.0, 27.0, 25.7, 25.34, 25.30, 23.2, 23.1, 20.0, 19.5, 19.4,
19.2, 18.3, 17.8, 17.5; IR (thin film) nmax 3291, 2965, 2929,
1652, 1624, 1558, 1458 cm21; CIHRMS [MþH]þ calcu-
lated for C28H41N4O3: 481.3180, found: 481.3178; [a]2D3¼
297.28 (c¼1.0, distilled CHCl3); [a]2D3¼21408 (c¼0.9,
distilled MeOH).
4.1.16. (12R,15S)-E-Terpeptin (32). Prepared from the
(12R,15S) stereoisomer of 24-E following the procedures
1
reported for 2. H NMR (400 MHz, CDCl3) d 8.10 (d, 1H,
J¼10.0 Hz), 8.00 (s, 1H), 7.75–7.73 (m, 1H), 7.38 (dd, 1H,
J¼10.8, 14.8 Hz), 7.26–7.23 (m, 1H), 7.13–7.07 (m, 2H),
6.39 (d, 1H, J¼14.8 Hz), 6.26 (d, 1H, J¼8.4 Hz), 5.31–5.27
(m, 1H), 4.82 (dd, 1H, J¼6, 8.4 Hz), 4.59 (d, 1H, J¼
10.8 Hz), 3.49 (d, 2H, J¼7.2 Hz), 3.10 (s, 3H), 2.44–2.35
(m, 1H), 2.00 (s, 3H), 1.77 (s, 3H), 1.71 (s, 3H), 1.04–0.85
(m, 12H); 13C NMR (75.0 MHz, CDCl3) d 174.1, 170.3,
166.2, 135.8, 135.6, 135.4, 126.6, 121.6, 120.1, 119.65
119.56, 110.5, 107.6, 107.0, 63.4, 54.4, 31.3, 31.1, 29.6,
25.9, 25.6, 25.3, 23.2, 19.9, 19.5, 18.8, 17.8, 17.3; IR (thin
film) nmax 3303, 2967, 2930, 2875, 1634, 1552, 1461, 1373,
1313, 1217, 1093 cm21; CIHRMS [MþH]þ calculated for
4.1.13. (12S,15R)-Z-Terpeptin (29). Prepared from the
(12S,15R) stereoisomer of 24-Z following the procedures
1
reported for 2. H NMR (400 MHz, DMSO-d6) d 10.98 (s,
1H), 8.63 (d, 1H, J¼10.4 Hz), 7.92 (d, 1H, J¼7.2 Hz), 7.30