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PAPER
Cat-CO-Leu-Leu-Leu-NHCH2-Cat (7c)
Yield: 438 mg (99%); light brown solid; mp 110 °C (dec.).
1 H), 6.60 (t, J = 7.7 Hz, 1 H), 4.48 (d, J = 7.8 Hz, 1 H), 4.34 (d,
J = 14.6 Hz, 1 H), 4.31 (d, J = 14.6 Hz, 1 H), 4.25 (d, J = 8.3 Hz, 1
H), 4.18 (d, J = 8.1 Hz, 1 H), 2.18 (m, 1 H), 2.01 (m, 2 H), 1.00–
0.84 (m, 18 H).
13C NMR (methanol-d4): = 173.8 (C), 173.7 (C), 173.5 (C), 170.4
(C), 149.6 (C), 149.2 (C), 147.1 (C), 146.6 (C), 144.5 (C), 126.1
(CH), 121.4 (CH), 120.5 (CH), 119.9 (CH), 119.8 (CH), 117.5 (C),
115.6 (CH), 60.4 (CH), 60.3 (CH), 60.2 (CH), 39.8 (CH2), 32.0
(CH), 32.0 (CH), 31.9 (CH), 19.9 (CH3), 19.6 (CH3), 19.1 (CH3),
19.0 (CH3), 19.0 (CH3), 18.8 (CH3).
1H NMR (methanol-d4): = 7.23 (dd, J = 8.1, 1.5 Hz, 1 H), 6.94
(dd, J = 7.8, 1.5 Hz, 1 H), 6.60–6.74 (m, 4 H), 4.61 (dd, J = 9.4, 5.2,
1 H), 4.40–4.45 (m, 2 H), 4.34 (s, 2 H), 1.55–1.76 (m, 9 H), 0.98 (d,
J = 6.1 Hz, 3 H), 0.95 (d, J = 6.2 Hz, 3 H), 0.86-0.92 (m, 12 H).
13C NMR (methanol-d4): = 175.1 (C), 174.9 (C), 174.5 (C), 171.0
(C), 149.6 (C), 147.2 (C), 146.6 (C), 144.5 (C), 126.1 (C), 121.2
(CH), 120.6 (CH), 119.8 (CH, double intensity), 119.7 (CH), 117.1
(C), 115.6 (CH), 53.7 (CH), 53.3 (CH), 53.0 (CH), 41.8 (CH2), 41.7
(CH2), 41.4 (CH2), 39.9 (CH2), 26.1 (CH), 25.8 (CH), 25.8 (CH),
23.4 (2 CH3), 23.4 (CH3), 22.1 (CH3), 22.0 (CH3), 21.9 (CH3).
IR (KBr): 3286, 3090, 2965, 1636, 1536, 1372, 1335, 1265, 1077,
743 cm–1.
IR (KBr): 3290, 3090, 2958, 2871, 1642, 1588, 1480, 1369, 1338,
1264, 1173, 1078, 948, 922, 847, 790, 741 cm-1.
MS (+FAB) m/z: 573 [MH+], 434, 335, 250, 236, 208, 151, 137,
123.
MS (+FAB, 3-NBA) m/z: 615 [MH+], 476, 363, 250, 222, 137.
HRMS m/z: [M+] calcd for C29H41N4O8 (573.67), 573.2924; found,
573.2908.
HRMS m/z: [M+] calcd for C32H47N4O8 (615.8), 615.3394; found,
615.3412.
Anal. Calcd for C29H40N4O8 2.5 H2O (618.7): C, 56.39; H, 7.34; N,
9.07. Found: C, 56.56; H, 6.93; N, 9.14.
Anal. calcd for C32H46N4O8 2 H2O (651.8): C, 59.06; H, 7.74; N,
8.61. Found: C, 59.28; H, 7.16; N, 8.38.
Preparation of Cat-CO-Ala-Val-Leu-NHCH2-Cat (7e)
Ver-CO-Ala-Val-Leu-OH (4e)
Yield: 1.12 g of a waxy slightly yellow solid which was pure
enough for further transformations; mp 65 °C.
Preparation of Cat-CO-Val-Val-Val-NHCH2-Cat (7d)
Ver-CO-Val-Val-Val-OH (4d)
Yield: 1.05 g of crude product which was pure enough for further
transformations.
1H NMR (methanol-d4): = 7.43 (dd, J = 1.8, 7.8 Hz, 1 H), 7.20
(dd, J = 1.8, 7.8 Hz, 1 H), 7.15 (t, J = 7.8 Hz, 1 H), 4.59 (m, 1 H),
4.35 (m, 1 H), 4.30 (m, 1 H), 3.31 (s, 3 H), 3.30 (s, 3 H), 2.16 (m, 2
H), 2.07 (m, 1 H), 0.98 (m, 18 H).
13C NMR (methanol-d4): = 174.5 (C), 173.7 (C), 173.5 (C), 167.6
(C), 154.3 (C), 149.0 (C), 127.9 (C), 125.4 (CH), 122.8 (CH), 117.0
(CH), 62.1 (CH3), 60.3 (CH), 60.0 (CH), 58.9 (CH), 56.6 (CH3),
32.8 (CH), 32.0 (CH), 31.7 (CH), 19.9 (CH3), 119.7 (CH3), 19.6
(CH3), 19.0 (CH3), 18.6 (CH3), 18.3 (CH3).
1H NMR (methanol-d4): = 7.42 (dd, J = 2.0, 7.5 Hz, 1 H), 7.15 (m,
2 H), 4.70 (q, J = 7.0 Hz, 1 H), 4.46 (t, J = 7.5 Hz, 1 H), 4.25 (d,
J = 7.6 Hz, 1 H), 3.90 (s, 3 H), 3.88 (s, 3 H), 2.11 (m, 1 H), 1.72 (m,
1 H), 1.65 (m, 2 H), 1.44 (d, J = 7.0 Hz, 3 H), 1.00 (d, J = 6.8 Hz, 3
H), 0.98 (d, J = 6.8 Hz, 3 H), 0.95 (d, J = 6.5 Hz, 3 H), 0.91 (d,
J = 6.4 Hz, 3 H).
13C NMR (methanol-d4): = 175.7 (C), 174.6 (C), 173.5 (C), 167.3
(C), 154.3 (C), 149.0 (C), 128.0 (C), 125.4 (CH), 122.6 (CH), 116.9
(CH), 61.9 (CH3), 60.0 (CH), 56.6 (CH3), 51.9 (CH), 50.5 (CH),
41.4 (CH2), 32.1 (CH), 25.9 (CH), 23.49 (CH3), 21.8 (CH3), 19.7
(CH3), 18.9 (CH3), 18.7 (CH3).
MS (EI, 70 eV) m/z: 479 ([M+], 0.2) 264 (29), 236 (33), 165 (100).
HRMS m/z: [M+] calcd. for C24H37N3O7, 479.2632; found,
MS (+FAB, 3-NBA) m/z: 466 [MH+], 448, 335, 236, 208, 165.
HRMS m/z: [M+] calcd for C23H36N3O7, 466.2553; found,
479.2622.
466.2532.
Ver-CO-Val-Val-Val-NHCH2-Ver (6d)
Ver-CO-Ala-Val-Leu-NHCH2-Ver (6e)
Yield: 985 mg [49% over two steps starting from H2N-Val-Val-Val-
OH (3d)] as a grey solid after recrystallization from CH2Cl2–
MeOH; mp 240 °C (dec.).
Yield: 730 mg (39% over two steps starting from H2N-Ala-Val-
Leu-OH 3e) as a beige solid after recrystallization from methanol;
mp: 173-180 °C.
1H NMR (CDCl3): = 8.80 (d, J = 7.0 Hz, 1 H), 8.01 (s br, 1 H),
7.95 (d, J = 8.2 Hz, 1 H), 7.41 (dd, J = 7.1, 2.4 Hz, 1 H), 7.11 (d,
J = 8.4 Hz, 1 H), 6.98–7.04 (m, 2 H), 6.84–6.92 (m, 2 H), 6.73 (dd,
J = 7.9, 1.7 Hz, 1 H), 5.2–5.05 (m, 1 H), 4.77–4.83 (m, 1 H), 4.39–
4.52 (m, 3 H), 3.86 (s, 3 H), 3.89 (s, 3 H), 3.79 (s, 3 H), 3.76 (s, 3
H), 2.11 (q, J = 6.8 Hz, 1 H), 1.65–1.75 (m, 3 H), 1.40 (d, J = 6.9
Hz, 3 H), 0.88–0.93 (m, 12 H).
1H NMR (CDCl3): = 8.74 (d, J = 8.4 Hz, 1 H), 8.14 (s br, 2 H),
7.32–7.34 (m, 1 H), 6.97–6.99 (m, 3 H), 6.85–6.89 (m, 2 H), 6.74
(dd, J = 7.2, 2.4 Hz, 1 H), 4.93 (dd, J = 15.6, 7.8 Hz, 1 H), 4.70 (dd,
J = 17.4, 8.7 Hz, 1 H), 4.43-4.48 (m, 3 H), 3.89 (s, 3 H), 3.86 (s, 3
H), 3.79 (s, 3 H), 3.76 (s, 3 H), 2.03–2.15 (m, 3 H), 0.97 (d, J = 6.7
Hz, 3 H), 0.95 (d, J = 6.8 Hz, 3 H), 0.94 (d, J = 6.8 Hz, 3 H), 0.92
(d, J = 6.8 Hz, 3 H), 0.88 (d, J = 6.7 Hz, 3 H), 0.87 (d, J = 6.6 Hz, 3
H).
13C NMR (CDCl3): = 172.9 (C), 172.3 (C), 171.3 (C), 164.9 (C),
152.6 (C), 152.4 (C), 147.9 (C), 146.8 (C), 132.0 (C), 125.9 (C),
124.2 (CH), 123.9 (CH), 122.5 (CH), 120.6 (CH), 115.7 (CH),
111.3 (CH), 61.3 (CH3), 60.6 (CH3), 58.7 (CH), 56.1 (CH3), 55.7
(CH3), 51.8 (CH), 49.5 (CH), 41.2 (CH2), 38.1 (CH2), 31.3 (CH),
24.9 (CH), 22.9 (CH3), 22.0 (CH3), 19.2 (CH3), 19.0 (CH3), 18.1
(CH3).
13C NMR (CDCl3): = 171.5 (2C), 171.3 (C), 165.0 (C), 152.6 (C),
152.4 (C), 147.8 (C), 146.9 (C), 132.0 (C), 126.5 (C), 124.1 (CH),
123.9 (CH), 122.5 (CH), 120.8 (CH), 115.4 (CH), 111.4 (CH), 61.5
(CH3), 60.6 (CH3), 58.7 (CH), 58.6 (CH), 58.4 (CH), 56.1 (CH3),
55.7 (CH3), 38.1 (CH2), 31.7 (CH), 31.7 (CH), 31.0 (CH), 19.3
(CH3), 19.2 (CH3), 19.0 (CH3), 18.7 (CH3), 18.5 (CH3), 18.3 (CH3).
IR (KBr): 3275, 3076, 2961, 2836, 1634, 1542, 1482, 1390, 1266,
1226, 1171, 1087, 1004, 748, 715 cm–1.
IR (KBr): 3281, 3068, 22957, 2873, 1630, 1580, 1545, 1477, 1432,
1388, 1311, 1268, 1230, 1170, 1151, 1091, 1068, 1002, 954, 817,
779, 746, 713 cm–1.
MS (+FAB, 3-NBA) m/z: 615 [MH+], 448, 335, 236, 165, 136.
Cat-CO-Val-Val-Val-NHCH2-Cat (7d)
Yield: 289 mg (96%); grey solid; mp 176–180 °C.
1H NMR (methanol-d4): = 7.34 (dd, J = 1.5, 8.1 Hz, 1 H), 6.93
(dd, J = 1.5, 7.9 Hz, 1 H), 6.71 (m, 2 H), 6.65 (dd, J = 1.5, 7.6 Hz,
HRMS m/z: [M+] calcd for C32H47N4O8, 615.3394; found,
615.3377.
Synthesis 2002, No. 1, 126–132 ISSN 0039-7881 © Thieme Stuttgart · New York