T. Sunazuka et al. / Bioorg. Med. Chem. 17 (2009) 2751–2758
2757
plex m, 3H, f position of MePhe, d1, d2 position of MePhe), 5.91
(complex m, 1H, b position of OAllyl), 5.31 (dd, J = 17.0, 5.0 Hz,
Ala), 1.29 (m, 1H,
c
position of Arg), 1.18 (m, 2H, b position of
Arg), 13C NMR (75 MHz, CD3OD) The mixture of rotamers was ob-
served. d: 175.2, 174.7, 174.6, 173.5, 172.1, 171.9, 171.7, 171.2,
156.2, 155.9, 139.4, 133.4, 130.8 (x2), 130.0 (x2), 129.6, 118.7,
66.7, 63.9, 50.8, 50.3, 48.9, 48.6, 41.8, 38.7, 36.7, 35.0, 30.3, 29.7,
28.5, 26.6, 22.5, 17.9, HR-MS (FAB, thioglycerol + glycerol,
PEG600+NaI) calcd for C34H50O12N9: 776.3579 [M+H], found m/z:
776.3579 [M+H]+.
1H,
of OAllyl) 5.06 (dd, J = 12.0, 3.0 Hz, 1H,
(m, 2H, of position of Asp2), 4.57 (dd, J = 5.0, 5.0 Hz, 1H,
tion of OAllyl), 4.30 (dd, J = 7.0, 2.0 Hz, 1H, position of Arg), 3.21
c
position of OAllyl), 5.21 (dd, J = 10.0, 1.0 Hz, 1H,
position of MePhe), 4.80
posi-
c position
a
a
a
a
(dd, J = 14.0, 2.0 Hz, 1H, b position of MePhe), 3.10–2.90 (complex
m, 3H, b position of MePhe, d position of Arg), 2.92 (m, 2H, b posi-
tion of Asp2), 2.86 (t, 3H, NMe of Arg), 2.78 (s, 1.5H, NMe of MePhe,
rotamer), 2.76 (s, 1.5H, NMe of MePhe, rotamer), 1.92 (s, 2H, Me of
x
4.12. N-Ac-Arg{N -(N-methylcarbanoyl)}-N-methyl-Phe-OH
Ac, rotamer), 1.89 (s, 1H, Me of Ac, rotamer), 1.61(m, 1H,
c
position
19a
of Arg), 1.28 (m, 1H, position of Arg), 1.16 (d, 2H, b position of
c
Arg), 13C NMR (75 MHz, CD3OD) The mixture of rotamers was ob-
served. d: 174.5, 174.2, 173.5, 171.7, 171.2, 155.9, 155.8, 139.4,
133.4, 130.8 (x2), 130.0 (x2), 129.6, 118.7, 66.6, 63.6, 50.4, 49.1,
42.0, 36.7, 35.1, 30.3, 30.0, 28.9, 26.6, 22.2, HR-MS (FAB, thioglyc-
erol + glycerol, PEG600+NaI) calcd for C27H40O8N7: 590.2957
[M+H], found m/z: 590.2938 [M+H]+.
IR (KBr) m
cmꢁ1: 3379, 3197, 3095, 3025, 1683, 1639, 1562,
1544, 1494, 1423, 1251, ½a D26
ꢂ
= –61.9 (c 1.0, MeOH), 1H NMR
(300 MHz, CD3OD) The mixture of rotamers was observed. d: 7.33
(dd, J = 7.0, 7.0 Hz, 2H,
plex m, 3H, f position of MePhe, d1, d2 position of MePhe), 5.02 (dd,
J = 12.0, 3.0 Hz, 1H, position of MePhe), 4.30 (dd, J = 7.0, 7.0 Hz,
1H, position of Arg), 3.24 (dd, J = 14.0, 7.0 Hz, 1H, b position of
e1, e2 position of MePhe), 7.28–7.18 (com-
a
a
x
4.10. N-Ac-
D
-Ala-Arg{N -(N-methylcarbanoyl)}-N-methyl-Phe-
MePhe), 3.10–3.00 (complex m, 3H, b position of MePhe, d position
of Arg), 2.91 (s, 3H, NMe of MePhe), 2.78 (s, 1.5H, NMe of Arg, rot-
amer), 2.76 (s, 1.5H, NMe of Arg, rotamer), 1.90 (s, 1H, Me of Ac,
Asp(OAllyl)-OH 18b
IR (KBr)
m
cmꢁ1: 3415, 3300, 3080, 2940, 1725, 1675, 1600,
rotamer), 1.89 (s, 2H, Me of Ac, rotamer), 1.64 (m, 1H,
c
position
1538, 1486, 1450, 1400, 1200, ½a D27
ꢂ
¼ ꢁ59:1 (c 1.0, MeOH), 1H
of Arg), 1.28 (m, 1H,
c position of Arg), 1.18 (m, 2H, b position of
NMR (300 MHz, CD3OD) The mixture of rotamers was observed. d:
Arg), 13C NMR (75 MHz, CD3OD) The mixture of rotamers was ob-
served. d: 173.6, 173.4, 172.7, 156.0, 155.8, 139.1, 130.5 (ꢀ2),
130.0 (ꢀ2), 129.5, 62.8, 49.1, 41.9, 35.2, 30.8, 29.9, 29.7, 26.5,
22.3, HR-MS (FAB, thioglycerol + glycerol, PEG600 + NaI), calcd for
C20H31O5N6: 435.2356 [M+H], found m/z: 435.2346 [M+H]+.
7.33 (dd, J = 7.0, 7.0 Hz, 2H, e1, e2 position of MePhe), 7.26–7.17
(complex m, 3H, f position of MePhe, d1, d2 position of MePhe),
5.91 (complex m, 1H, b position of OAllyl), 5.30 (dd, J = 17.0,
11.0 Hz, 1H,
position of OAllyl), 5.11 (dd, J = 12.0, 4.0 Hz, 1H,
MePhe), 4.78 (m, 1H, position of Asp2), 4.57 (dd, J = 11.0 Hz,
6.0 Hz, 2H, of position of OAllyl), 4.28 (m, 2H, position of Ala,
position of Arg), 3.21 (dd, J = 14.0, 3.0 Hz, 1H, b position of
c
position of OAllyl), 5.22 (dd, J = 11.0, 7.0 Hz, 1H,
c
a
position of
x
a
4.13. N-Ac-
D
-Ala-Arg{N -(N-methylcarbanoyl)}-N-methyl-Phe-
a
a
OH 19b
a
MePhe), 3.10–2.92 (complex m, 3H, b position of MePhe, d position
of Arg), 2.69 (s, 2H, NMe of MePhe), 2.67 (s, 1H, NMe of MePhe, rot-
amer), 2.88 (s, 3H, NMe of Arg), 2.83 (m, 2H, b position of Asp2),
1.89 (s, 1H, Me of Ac, rotamer), 1.87 (s, 2H, Me of Ac, rotamer),
IR (KBr) m
cmꢁ1: 3328, 3100, 3000, 2900, 1677, 1641, 1560,
1540, 1442, 1417, 1376, 1200,
NMR (300 MHz, CD3OD) The mixture of rotamers was observed. d:
½
a 2D6
ꢂ
¼ ꢁ31:4 (c 1.0, MeOH), 1H
7.34 (dd, J = 7.0, 7.0 Hz, 2H,
(complex m, 3H, f position of MePhe, d1, d2 position of MePhe),
5.15 (dd, J = 11.0, 5.0 Hz, 1H, position of MePhe), 4.24 (m, 2H,
position of Ala, position of Arg), 3.11 (dd, J = 12.0, 4.0 Hz, 1H, b
e1, e2 position of MePhe), 7.30–7.18
1.52 (m, 1H,
of Ala), 1.16 (m, 1H,
c
position of Arg), 1.20 (d, J = 6.7 Hz, 3H, b position
position of Arg), 1.03 (m, 2H, b position of
c
a
a
Arg), 13C NMR (75 MHz, CD3OD) The mixture of rotamers was ob-
served. d: 175.2, 174.2, 173.5, 172.1, 171.7, 171.1, 156.0, 155.8,
139.2, 133.4, 130.8 (ꢀ2), 129.6 (ꢀ2), 129.6, 118.8, 66.7, 63.5,
49.8, 49.1, 48.6, 42.0, 36.8, 35.2, 30.3, 29.8, 28.9, 26.6, 22.6, 18.0,
HR-MS (FAB, thioglycerol + glycerol, PEG600+NaI), calcd for
C30H45O9N8: 661.3345 [M+H], found m/z: 661.3310 [M+H]+.
a
position of MePhe), 3.17–3.00 (complex m, 3H, b position of
MePhe, d position of Arg), 2.96 (s, 3H, NMe of MePhe), 2.80 (s,
1H, NMe of Arg, rotamer), 2.77 (s, 2H, NMe of Arg, rotamer), 2.00
(s, 2H, Me of Ac, rotamer), 1.97 (s, 1H, Me of Ac, rotamer), 1.61
(m, 1H,
Ala), 1.23 (m, 1H,
c
position of Arg), 1.30 (d, J = 4.0 Hz, 3H, b position of
position of Arg), 1.09 (m, 2H, b position of
c
x
4.11. N-Ac-Asp-
D
-Ala-Arg{N -(N-methylcarbanoyl)}-N-methyl-
Arg), 13C NMR (75 MHz, CD3OD) The mixture of rotamers was ob-
served. d: 174.8, 173.8, 173.3, 173.2, 156.0, 155.8, 138.9, 130.6
(ꢀ2), 130.0 (ꢀ2), 129.5, 64.5, 48.9, 48.6, 41.9, 35.3, 30.8, 29.8,
28.8, 26.6, 22.4, 18.0, HR-MS (FAB, thioglycerol + glycerol,
PEG600 + NaI), calcd for C23H36O6N7: 506.2727 [M+H], found m/z:
506.2716[M+H]+.
Phe-Asp(OAllyl)-OH 18c
IR (KBr)
m
cmꢁ1: 3423, 3300, 3000, 2900, 1725, 1670, 1600,
1536, 1500, 1434, 1396, 1200, ½a D27
ꢂ
¼ ꢁ28:1 (c 1.0, MeOH), 1H
NMR (300 MHz, CD3OD) The mixture of rotamers was observed. d:
7.32 (dd, J = 7.0, 7.0 Hz, 2H, e1, e2 position of MePhe), 7.23–7.17
(complex m, 3H, f position of MePhe, d1, d2 position of MePhe),
x
4.14. N-Ac-Asp-
D
-Ala-Arg{N -(N-methylcarbanoyl)}-N-methyl-
5.91 (complex m, 1H, b position of OAllyl), 5.31 (dd, J = 17.0,
Phe-OH 19c
7.0 Hz, 1H,
sition of OAllyl), 5.08 (dd, J = 11.0, 3.0 Hz, 1H,
4.86 (m, 1H, position of Asp2), 4.73 (dd, J = 11.0, 5.0 Hz, 1H,
sition of Asp1), 4.58 (dd, J = 6.0 Hz, 6.0 Hz, 2H, of position of OAl-
lyl), 4.36 (m, 2H, position of Ala, position of Arg), 3.22 (dd,
J = 14.0, 3.0 Hz, 1H, b position of MePhe), 3.04 (dd, J = 13.0,
4.0 Hz, 2H, b position of Asp1), 3.01–2.97 (complex m, 3H, b posi-
tion of MePhe, d position of Arg), 2.92 (m, 2H, b position of Asp2),
2.85 (s, 3H, NMe of MePhe,), 2.77 (s, 1.5H, NMe of Arg, rotamer),
2.76 (s, 1.5H, NMe of Arg, rotamer), 1.99 (s, 3H, Me of Ac), 1.62
c
position of OAllyl), 5.21 (dd, J = 10.0, 2.0 Hz, 1H,
position of MePhe),
po-
c po-
a
IR (KBr) m
cmꢁ1: 3415, 3100, 3000, 2900, 1720, 1676, 1583,
a
a
1539, 1486, 1435, 1400, 1201, ½a D27
ꢂ
¼ ꢁ38:1 (c 1.0, MeOH), 1H
a
NMR (300 MHz, CD3OD) The mixture of rotamers was observed. d:
a
a
7.32 (dd, J = 7.0, 7.0 Hz, 2H,
(complex m, 3H, f position of MePhe, d1, d2 position of MePhe),
5.04 (dd, J = 11.0, 3.0 Hz, 1H, position of MePhe), 4.78 (dd,
J = 10.0, 6.0 Hz, 1H, position of Asp1), 4.25 (m, 2H, position of
Ala, position of Arg), 3.24 (dd, J = 12.0, 6.0 Hz, 1H, b position of
e1, e2 position of MePhe), 7.26–7.18
a
a
a
a
MePhe), 3.12 (dd, J = 12.0, 6.0 Hz, 2H, b position of Asp1), 3.08–
(m, 1H,
c position of Arg), 1.32 (d, J = 6.7 Hz, 3H, b position of
2.99 (complex m, 3H, b position of MePhe, d position of Arg),