(m, 2H, NHCH), 4.37 (m, 1H, NHCH), 4.51 (m, 1H, NHCH),
4.83 (m, 1H, NHCH), 4.98 (m, 2H, CH2-Ph), 7.13 (s, 2H, NH2),
7.32 (m, 8H, CH-Ph, CH-His), 7.62 (d, J = 8.07 Hz, 1H, NH),
7.74 (d, J = 8.13 Hz, 1H, NH), 7.97 (m, 2H, NH), 8.33 (m, 2H,
NH), 8.95 (m, 3H, CH-His), 14.25 (s, 3H, NH-His); 13C NMR
(126 MHz, DMSO-d6) dC(ppm): 24.65 (HH2-Pro), 24.74 (HH3-
Aib), 25.15 (HH3-Aib), 26.14 (HH2-Pro), 26.35 (HH2-His), 27.07
(HH2-His), 28.82 (HH2-His), 41.97 (HH2-Gly), 42.38 (HH2-Gly),
47.33 (HH2-Pro), 50.20 (HH), 52.23 (HH), 53.65 (HH), 55.41
(HH), 56.10 (Hq-Aib), 60.58 (HH-Pro), 61.61 (HH2-Ser), 65.71
(HH2-Ph), 117.03 (HH-His), 117.09 (HH-His), 117.36 (HH-His),
127.60 (HH-Ph), 127.88 (HH-Ph), 128.41 (HH-Ph), 129.13 (Hq-
His), 129.55 (Hq-His), 129.80 (Hq-His), 133.81 (HH-His), 133.86
(HH-His), 133.90 (HH-His), 136.80 (Hq-Ph), 155.98 (Hq-Bn),
(d, J = 7.77 Hz, 1H, NH), 7.92 (t, 1H, NH-Gly), 7.97 (d, J =
7.89 Hz, 1H, NH), 8.09 (d, J = 8.17 Hz, 1H, NH), 8.23 (t, 1H,
NH-Gly), 8.27 (s, 1H, NH), 8.95 (m, 3H, CH-His), 14.25 (s, 3H,
NH-His); 13C NMR (126 MHz, DMSO-d6) dC(ppm): 24.58 (HH2-
Pro), 24.78 (HH3-Aib), 24.90 (HH3-Aib), 25.74 (HH2-Pro), 26.22
(HH2-His), 26.68 (HH2-His), 28.8 (HH2-His), 36.29 (CH2-Asp),
42.10 (HH2-Gly), 42.39 (HH2-Gly), 47.28 (HH2-Pro), 50.28 (HH),
51.45 (HH), 51.76 (HH), 52.37 (HH), 56.03 (Hq-Aib), 60.54 (HH-
Pro), 65.71 (HH2-Ph), 116.86 (HH-His), 117.03 (HH-His), 117.27
(HH-His), 127.77 (HH-Ph), 127.88 (HH-Ph), 128.38 (HH-Ph),
129.13 (Hq-His), 129.57 (Hq-His), 129.90 (Hq-His), 133.73 (HH-
His), 133.79 (HH-His), 133.87 (HH-His), 136.76 (Hq-Ph), 156.01
(Hq-Bn), 168.97 (Hq), 170.77 (Hq), 171.50 (Hq), 171.80 (Hq),
-1
˜
171.89 (Hq), 172.42 (Hq), 174.76 (Hq); IR: (KBr-pellet) n [cm ] =
168.98 (Hq), 169.07 (Hq), 170.73 (Hq), 170.79 (Hq), 172.01 (Hq),
3311.18, 3152.08, 3037.34, 2882.09, 2639.11, 1671.98, 1541.81,
1432.85, 1249.65, 1203.36, 1135.87, 835.99, 799.35, 722.21, 627.72;
HR-MS (pos. ESI): m/z calcd. for C43H55N15NaO12 [M + Na]+:
-1
˜
172.32 (Hq), 174.52 (Hq); IR: (KBr-pellet) n [cm ] = 3297.69,
+
3150.15, 3039.26, 2927.41, 2878.24, 2634.29, 1671.02, 1542.77,
1432.85, 1254.47, 1202.40, 1134.90, 835.99, 799.35, 721.25, 627.72;
996.405, found: 996.406.
+
HR-MS (pos. ESI): m/z calcd. for C42H55N15NaO11 [M + Na]+:
968.410, found: 968.410.
CbzNH-L-Ser-Gly-L-His-D-Pro-Aib-L-His-Gly-L-Ser-NH2 (1e)
Yield: 257 mg (0.29 mmol, 82%); mp 134 ◦C; 1H NMR (500 MHz,
DMSO-d6) dH(ppm): 1.24 (s, 3H, CH3-Aib), 1.29 (s, 3H, CH3-
Aib), 1.79 (m, 2H, CH2-Pro), 1.92 (m, 1H, CH2-Pro), 2.06 (m, 1H,
CH2-Pro), 2.92 (m, 1H, CH2-His), 3.11 (m, 2H, CH2-His), 3.24 (m,
1H, CH2-His), 3.71 (m, 10H, CH2-Gly, CH2-Pro, CH2-Ser), 4.07
(m, 1H, NHCH), 4.20 (m, 2H, NHCH), 4.49 (m, 1H, NHCH),
4.76 (m, 1H, NHCH), 5.02 (m, 2H, CH2-Ph), 7.29 (m, 9H, CH-Ph,
CH-His, NH2), 7.71 (d, J = 7.95 Hz, 1H, NH), 7.96 (t, 1H, NH-
Gly), 8.07 (m, 1H, NH), 8.24 (m, 2H, NH), 8.39 (m, 1H, NH), 8.95
(m, 2H, CH-His), 14.39 (s, 2H, NH-His); 13C NMR (126 MHz,
DMSO-d6) dC(ppm): 24.62 (HH2-Pro), 24.85 (HH3-Aib), 25.01
(HH3-Aib), 26.13 (HH2-Pro), 26.20 (HH2-His), 28.80 (HH2-His),
42.07 (HH2-Gly), 42.31 (HH2-Gly), 47.31 (HH2-Pro), 50.29 (HH),
52.19 (HH), 55.35 (HH), 56.09 (Hq-Aib), 57.13 (HH), 60.69 (HH-
Pro), 61.61 (HH2-Ser), 61.74 (HH2-Ser), 65.66 (HH2-Ph), 117.10
(HH-His), 117.32 (HH-His), 127.79 (HH-Ph), 127.87 (HH-Ph),
128.38 (HH-Ph), 129.07 (Hq-His), 129.70 (Hq-His), 133.76 (HH-
His), 133.87 (HH-His), 136.85 (Hq-Ph), 156.05 (Hq-Bn), 168.97
CbzNH-L-His-Gly-L-His-D-Pro-Aib-L-His-Gly-L-Glu-NH2 (1c)
Yield: 298 mg (0.30 mmol, 86%); mp 136 ◦C; 1H NMR (500 MHz,
DMSO-d6) dH(ppm): 1.23 (s, 3H, CH3-Aib), 1.27 (s, 3H, CH3-
Aib), 1.77 (m, 3H, CH2-Pro, CH2-Glu), 1.98 (m, 3H, CH2-Pro,
CH2-Glu), 2.24 (m, 2H, CH2-Pro, CH2-Glu), 2.93 (m, 2H, CH2-
His), 3.14 (m, 3H, CH2-His), 3.24 (m, 1H, CH2-His), 3.77 (m, 6H,
CH2-Gly, CH2-Pro), 4.19 (m, 2H, NHCH), 4.40 (m, 2H, NHCH),
4.83 (m, 1H, NHCH), 4.97 (m, 2H, CH2-Ph), 7.31 (m, 10H, CH-
Ph, CH-His, NH2), 7.62 (d, J = 8.35 Hz, 1H, NH), 7.81 (d, J =
7.77 Hz, 1H, NH), 7.87 (d, J = 7.96 Hz, 1H, NH), 7.94 (t, 1H,
NH-Gly), 8.34 (m, 2H, NH), 8.95 (m, 3H, CH-His); 13C NMR
(126 MHz, DMSO-d6) dC(ppm): 24.61 (HH2-Pro), 24.68 (HH3-
Aib), 25.06 (HH3-Aib), 25.87 (HH2-Pro), 26.35 (HH2-His), 27.06
(HH2-His), 27.31 (HH2-Glu), 28.84 (HH2-His), 30.20 (HH2-Glu),
41.95 (HH2-Gly), 42.37 (HH2-Gly), 47.32 (HH2-Pro), 50.16 (HH),
52.07 (HH), 52.50 (HH), 53.64 (HH), 56.05 (Hq-Aib), 60.43 (HH-
Pro), 65.70 (HH2-Ph), 117.07 (HH-His), 117.10 (HH-His), 117.34
(HH-His), 127.60 (HH-Ph), 127.87 (HH-Ph), 128.39 (HH-Ph),
129.09 (Hq-His), 129.54 (Hq-His), 129.84 (Hq-His), 133.82 (HH-
His), 133.90 (HH-His), 133.94 (HH-His), 136.78 (Hq-Ph), 155.96
(Hq-Bn), 168.92 (Hq), 168.99 (Hq), 170.70 (Hq), 170.78 (Hq),
(Hq), 169.06 (Hq), 170.71 (Hq), 170.89 (Hq), 171.95 (Hq), 172.19
-1
˜
(Hq), 174.42 (Hq); IR: (KBr-pellet) n [cm ] = 3308.29, 3152.08,
3039.26, 2931.27, 2882.09, 2635.25, 1671.98, 1541.81, 1437.67,
1249.65, 1203.36, 1134.90, 1081.87, 835.99, 800.31, 722.21, 627.72;
HR-MS (pos. ESI): m/z calcd. for C39H53N13NaO12 [M + Na]+:
+
172.46 (Hq), 173.20 (Hq), 173.92 (Hq), 173.95 (Hq), 174.74 (Hq);
-1
˜
IR: (KBr-pellet) n [cm ] = 3297.68, 3152.08, 3038.30, 2931.27,
918.383, found: 918.383.
2878.24, 2640.07, 1670.05, 1541.81, 1437.67, 1254.47, 1202.40,
1134.90, 835.03, 799.35, 721.25, 628.68; HR-MS (pos. ESI): m/z
calcd. for C44H57N15NaO12+ [M + Na]+: 1010.420, found: 1010.422.
CbzNH-L-Ser-Gly-L-Ser-D-Pro-Aib-L-His-Gly-L-His-NH2 (1f)
Yield: 254 mg (0.28 mmol, 81%); mp 162 ◦C; 1H NMR (500 MHz,
DMSO-d6) dH(ppm): 1.23 (s, 3H, CH3-Aib), 1.26 (s, 3H, CH3-
Aib), 1.81 (m, 2H, CH2-Pro), 1.92 (m, 1H, CH2-Pro), 2.05 (m, 1H,
CH2-Pro), 2.98 (m, 2H, CH2-His), 3.18 (m, 2H, CH2-His), 3.68 (m,
10H, CH2-Gly, CH2-Pro, CH2-Ser), 4.07 (m, 1H, NHCH), 4.25
(m, 1H, NHCH), 4.42 (m, 1H, NHCH), 4.49 (m, 1H, NHCH),
4.57 (m, 1H, NHCH), 5.02 (m, 2H, CH2-Ph), 7.32 (m, 9H, CH-
Ph, CH-His, NH2), 7.80 (d, J = 7.71 Hz, 1H, NH), 7.89 (m,
1H, NH), 8.02 (t, 1H, NH-Gly), 8.17 (t, 1H, NH-Gly), 8.28
(d, J = 4.97 Hz, 1H, NH), 8.97 (m, 2H, CH-His), 14.40 (s,
4H, NH-His); 13C NMR (126 MHz, DMSO-d6) dC(ppm): 24.50
CbzNH-L-Asp-Gly-L-His-D-Pro-Aib-L-His-Gly-L-His-NH2 (1d)
Yield: 236 mg (0.24 mmol, 69%); mp 114 ◦C; 1H NMR (500 MHz,
DMSO-d6) dH(ppm): 1.25 (s, 3H, CH3-Aib), 1.26 (s, 3H, CH3-
Aib), 1.82 (m, 2H, CH2-Pro), 1.90 (m, 1H, CH2-Pro), 2.05 (m,
1H, CH2-Pro), 2.68 (m, 1H, CH2-Asp), 2.94 (m, 3H, CH2-His),
3.13 (m, 4H, CH2-His, CH2-Asp), 3.67 (m, 6H, CH2-Gly, CH2-
Pro), 4.21 (m, 1H, NHCH), 4.36 (m, 1H, NHCH), 4.43 (m, 1H,
NHCH), 4.50 (m, 2H, NHCH), 5.02 (m, 2H, CH2-Ph), 7.34 (m,
10H, CH-Ph, NH2, CH-His), 7.66 (d, J = 7.56 Hz, 1H, NH), 7.85
4366 | Org. Biomol. Chem., 2009, 7, 4362–4368
This journal is
The Royal Society of Chemistry 2009
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