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Chapter 6
1.41 (s, 9H, Boc methyl groups), 1.78-1.35 (m, 6H, CH 2 lysine side chain). 13 C NMR (75
MHz, CDCl 3 ) δ (ppm): 172.9, 156.1, 155.6, 134.3, 133.4, 129.6, 129.4, 129.2, 126.7, 79.6,
63.7, 61.5, 49.9, 40.7, 32.5, 32.0, 29.1, 28.3, 22.3. ESI-MS (CH 3 OH, positive ions): calculated
m/z: 480.5 (MNa + ), found: 480.1
Compound 4 (N α -Boc-L-Lys-N ω -2-Cl-Z-aldehyde).Yield: 78%. 1 H NMR (300MHz ,
CDCl 3 ): δ (ppm) 9.54 (s, 1H, CH aldehyde), 7.43-7.20 (m, 4H, CH aromatic 2-Cl-Z group),
5.18 (s, 2H, CH 2 2-Cl-Z group), 5.09 (bs, 1H, N ω -H lysine side chain), 4.20 (sb, 1H N α -H),
3.74 (s, 1H, CHα), 3.26-3.09 (m, 2H, CH 2 lysine side chain), 1.65-1.47 (m, 2H, CH 2 lysine
side chain), 1.47-1.30 (m, 4H, CH 2 lysine side chain) 1.42 (s, 9H, Boc methyl groups). 13 C
NMR ( 75 MHz, CDCl 3 ): δ (ppm) 199.9, 156.3, 155.7, 134.2, 133.5, 129.7, 129.3, 128.5,
126.9, 80.1, 63.8, 59.5, 40.4, 32.5, 29.4, 28.3, 22.1. ESI-MS (CH 3 OH, positive ions):
calculated m/z: 453.89, found: 453.3
Compound 5 (a- N α -Boc-L-Lysψ-(N ω -2-Cl-Z)-L-Val methyl ester, b- N α -Boc-L-Lysψ-
(N ω -2-Cl-Z)-L-Arg-(N ω -Tosyl) methyl ester). Compound 5 a: Yield: 31%. 1 H NMR
(300MHz, CDCl 3 ): δ (ppm) 7.46-7.19 (m, 4H, CH aromatic 2-Cl-Z group), 5.20 (s, 2H, CH 2
2-Cl-Z group), 4.93 (bs, 1H, N ω -H lysine side chain), 4.58 (sb, 1H, N α -H), 3.70 (s, 3H, CH 3
methyl ester), 3.54 (bs, 1H, C(2)Hα), 3.24-3.10 (m, 2H, CH 2 lysine side chain), 2.98-2.87 (m,
1H, C(5)Hα), 2.72-2.28 (m, 2H, Lysψ CH 2 ), 1.60-1.21 (7H, m, CH 2 lysine side chain, CH
valine side chain), 1.42 ( s, 9H, CH 3 Boc group), 0.91 (d, 6H, J(H,H) = 6.6 Hz, CH 3 valine
side chain) 13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 175.3, 156.3, 156.2, 138.3, 129.6, 129.2,
128.6, 126.9, 125.7, 79.5, 64.2, 62.5, 52.3, 51.5, 50.6, 40.7, 32.5, 31.4, 29.8, 28.3, 22.8, 19.1,
18.6; ESI-MS (CH 3 OH, positive ions): calculated m/z: 515.0 (MH + ), 537.0 (MNa + ), 553.0
(MK + ), found: 514.4, 536.4, 552.4. Compound 5 b: Yield: 30%. 1 H NMR (300MHz, CDCl 3 ):
δ (ppm) 7.74 (d, 2H, J(H,H) = 8.1 Hz, CH aromatic tosyl group), 7.42-7.20 (m, 4H, CH
aromatic 2-Cl-Z group), 7.20 (d, 2H, J(H,H) = 8.1 Hz, CH aromatic tosyl group), 6.46 (bs,
2H, N-Hη arginine side chain), 5.11 (bs, 2H, CH 2 2-Cl-Z group), 3.68 (s, 3H, CH 3 methyl
ester), 3.51 (bs, 1H, C(2)Hα), 3.25-3.10 (m, 5H, CH 2 arginine side chain + lysine side chain +
C(5)H α), 2.77-2.31 (m, 2H, Lysψ CH 2 ), 2.36 (s, 3H, CH 3 tosyl group), 1.89-1.21 (m, 10H,
CH 2 arginine side chain, CH 2 lysine side chain), 1.38 ( s, 9H, CH 3 Boc group. 13 C NMR (75
MHz, CDCl 3 ): δ (ppm) 175.1, 156.7, 156.4, 156.2, 141.7, 140.9, 134.2, 133.1, 129.4, 129.3,
129.1, 129.0, 126.7, 125.8, 79.2, 63.7, 60.8, 51.8, 51.6, 50.8, 40.7, 40.5, 32.2, 29.6, 29.4, 28.3,
25.5, 22.6, 21.3. ESI-MS (CH 3 OH, positive ions): calculated m/z: 725.3 (MH + ), 747.3
(MNa + ); found: 725.4, 747.4
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