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Organic & Biomolecular Chemistry
CH(CH3)2, 6H), 1.93–2.06 (m, CH(CH3)2, 1H), 3.46 (s, 124.84, 127.48, 128.08, 128.64, 129.71, 137.76, 141.15, 143.84,
NCH3, 3H), 4.10–4.32 (m, CHFmoc, CH2Fmoc, 3H), 4.45 (app t, 143.98, 156.88, 173.71. Anal. Calcd for C31H27N3O7S (585.63):
J = 7.8 Hz, α-CH, 1H), 7.23–7.44 (m, Ar-HFmoc, 4H), 7.51–7.53 C, 63.88; H, 5.19; N, 6.98%. Found: C, 64.14; H, 5.20; N,
(m, Ar-HFmoc, 2H), 7.81–7.90 (m, Ar-HFmoc, NH, 3H), 8.20 6.96%.
(d, J = 8.7 Hz, Ar-HNs, 2H), 8.35 (d, J = 8.7 Hz, Ar-HNs, 2H).
13C NMR (75 MHz, DMSO-d6) δ 18.35, 19.13, 30.61, 34.02, amide (5g). Yield: 84%. H NMR (300 MHz, DMSO-d6) δ 1.05
47.02, 58.94, 66.36, 120.56, 124.76, 127.48, 128.08, 129.89, (s, C(CH3)3, 9H), 3.34 (s, NCH3, 3H), 4.12–4.32 (m, CHFmoc
141.18, 144.12, 144.20, 150.73, 174.01. Anal. Calcd for CH2Fmoc, 3H), 4.39–4.49 (m, CH2OtBu, 2H), 4.67–4.76 (m,
C27H27N3O7S (537.58): C, 60.32; H, 5.06; N, 7.82%. Found: C, α-CH, 1H), 7.27–7.34 (m, Ar-HFmoc 2H), 7.36–7.45 (m,
60.56; H, 5.06; N, 7.80%. Ar-HFmoc, 2H), 7.58–7.71 (m, Ar-HFmoc, NH, 3H), 7.90 (d, J =
N-Fmoc-O-tBu-L-serinyl-N-methyl-4-nitrobenzenesulfon-
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,
,
N-Fmoc-L-phenylalanyl-N-methyl-4-nitrobenzenesulfonamide 7.5 Hz, Ar-HFmoc, 2H), 8.18 (d, J = 8.9 Hz, Ar-HNs, 2H), 8.37 (d, J =
(5b). Yield: 86%. 1H NMR (300 MHz, CDCl3) δ 2.60–2.98 (m, 8.9 Hz, Ar-HNs, 2H). 13C NMR (75 MHz, DMSO-d6) δ 27.93,
CH2Ph, 2H), 3.20 (s, NCH3, 3H), 4.05–4.16 (m, CHFmoc, 1H), 34.01, 46.96, 53.90, 60.21, 66.88, 73.59, 120.57, 124.71, 127.51,
4.20–4.40 (m, α-CH, CH2Fmoc, 3H), 5.48 (br s, NH, 1H), 128.10, 130.01, 141.18, 144.12, 150.96, 156.67, 182.11. Anal.
7.10–7.45 (m, Ar-HFmoc, Ar-HPhe, 9H), 7.48 (d, J = 7.5 Hz, Calcd for C29H31N3O8S (581.64): C, 59.88; H, 5.37; N, 7.22%.
Ar-HFmoc, 2H), 7.86 (d, J = 7.5 Hz, Ar-HFmoc, 2H), 8.17 (d, J = 8.9 Found: C, 60.11; H, 5.35; N, 7.24%.
Hz, Ar-HNs, 2H), 8.36 (d, J = 8.9 Hz, Ar-HNs, 2H). 13C NMR
(75 MHz, CDCl3) δ 33.23, 39.15, 46.93, 55.35, 67.30, 120.07, amide (5h). Yield: 85%. H NMR (300 MHz, CDCl3) δ 1.35 (s,
124.41, 124.98, 127.08, 127.75, 127.80, 128.82, 129.32, 129.36, CH(CH3)3, 9H), 2.84–2.95 (m, CH2Tyr, 1H), 3.04–3.11 (m,
N-Fmoc-O-tBu-L-tyrosinyl-N-methyl-4-nitrobenzenesulfon-
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135.09, 141.28, 143.53, 143.60, 150.81, 156.98, 173.41. Anal. CH2Tyr, 1H), 3.18 (s, NCH3, 3H), 4.08–4.50 (m, CHFmoc
Calcd for C31H27N3O7S (585.63): C, 63.88; H, 5.19; N, 6.98%. CH2Fmoc, 3H), 4.61–4.68 (m, α-CH, 1H), 5.40 (d, J = 8.7 Hz, NH,
Found: C, 64.12; H, 5.21; N, 6.95%. 1H), 6.91 (d, J = 8.7 Hz, Ar-HTyr, 2H), 7.09 (d, J = 8.7 Hz,
,
N-Fmoc-L-alanyl-N-methyl-4-nitrobenzenesulfonamide (5c, l). Ar-HTyr, 2H), 7.22–7.43 (m, Ar-HFmoc, 4H), 7.53 (d, J = 7.2 Hz,
Yield: 92%. 1H NMR (300 MHz, CDCl3) δ 1.48 (d, J = 6.9 Hz, Ar-HFmoc, 2H), 7.80 (d, J = 7.2 Hz, Ar-HFmoc, 2H), 8.19 (d, J =
CH(CH3), 3H), 3.32 (s, NCH3, 3H), 4.09–4.27 (m, CHFmoc, 1H), 8.9 Hz, Ar-HNs, 2H), 8.35 (d, J = 8.9 Hz, Ar-HNs, 2H). 13C NMR
4.34 (d, J = 7.2 Hz, CH2Fmoc, 2H), 5.10–5.23 (m, α-CH, 1H), 5.36 (75 MHz, CDCl3) δ 29.01, 33.18, 38.65, 46.94, 55.36, 60.42,
(d, J = 9.0 Hz, NH, 1H), 7.25–7.46 (m, Ar-HFmoc, 4H), 7.65 (d, 67.31, 120.06, 124.21, 125.00, 127.08, 127.80, 129.53, 129.81,
J = 7.5 Hz, Ar-HFmoc, 2H), 7.81 (d, J = 7.5 Hz, Ar-HFmoc, 2H), 141.28, 143.54, 143.76, 150.66, 154.81, 155.86, 173.52. Anal.
8.26 (d, J = 9.0 Hz, Ar-HNs, 2H), 8.38 (d, J = 9.0 Hz, Ar-HNs, 2H). Calcd for C35H35N3O8S (657.73): C, 64.17; H, 5.83; N, 6.24%.
13C NMR (75 MHz, CDCl3) δ 18.88, 33.27, 47.01, 50.29, 67.24, Found: C, 64.37; H, 5.85; N, 6.26%.
120.06, 124.47, 125.00, 127.07, 127.81, 129.42, 141.30, 143.02,
N-Fmoc-O-tBu-L-glutamyl-N-methyl-4-nitrobenzenesulfon-
143.86, 155.87, 174.60. Anal. Calcd for C25H23N3O7S (509.53): amide (5i). Yield: 87%. 1H NMR (300 MHz, DMSO-d6) δ 1.38 (s,
C, 58.93; H, 4.55; N, 8.25%. Found: C, 58.72; H, 4.57; N, CH(CH3)3, 9H), 1.74–2.02 (m, CH2Glu, 2H), 2.19–2.31 (m,
8.22%.
CH2Glu, 2H), 3.33 (s, NCH3, 3H), 4.02–4.33 (m, α-CH, CHFmoc,
N-Fmoc-L-leucinyl-N-methyl-4-nitrobenzenesulfonamide CH2Fmoc, 4H), 7.25–7.44 (m, Ar-HFmoc, 4H), 7.73 (d, J = 7.5 Hz,
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(5d). Yield: 90%. H NMR (300 MHz, CDCl3) δ 0.94–1.07 (m, Ar-HFmoc, 2H), 7.80–7.95 (m, Ar-HFmoc, 2H), 7.96 (d, J = 8.9 Hz,
CH(CH3)2, 6H), 1.47–1.85 (m, CH2CH(CH3)2, 3H), 3.32 (s, NH 1H), 8.21 (d, J = 8.7 Hz, Ar-HNs, 2H), 8.38 (d, J = 8.7 Hz,
NCH3, 3H), 4.13–4.21 (m, CHFmoc, 1H), 4.28–4.43 (m, CH2Fmoc
2H), 5.10–5.30 (m, NH, α-CH, 2H), 7.27–7.34 (m, Ar-HFmoc
2H), 7.37–7.42 (m, Ar-HFmoc, 2H), 7.56 (d, J = 7.2 Hz, Ar-HFmoc
,
,
,
Ar-HNs, 2H). 13C NMR (75 MHz, DMSO-d6) δ 26.76, 28.20, 30.61,
47.11, 53.01, 66.20, 80.05, 120.58, 126.05, 127.51, 128.09,
141.21, 144.56, 154.89, 157.81, 176.21, 178.16. Anal. Calcd for
2H), 7.77 (d, J = 7.2 Hz, Ar-HFmoc, 2H), 8.25 (d, J = 8.7 Hz, C31H33N3O9S (623.67): C, 59.70; H, 5.33; N, 6.74%. Found:
Ar-HNs, 2H), 8.36 (d, J = 8.7 Hz, Ar-HNs, 2H). 13C NMR (75 MHz, C, 59.76; H, 5.34; N, 6.72%.
CDCl3) δ 21.06, 23.37, 24.92, 33.26, 41.72, 47.04, 53.04, 67.18,
N-Fmoc-D-valinyl-N-methyl-4-nitrobenzenesulfonamide
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120.05, 124.45, 124.98, 127.06, 127.82, 129.43, 141.30, 143.55, (5k). Yield: 82%. H NMR (300 MHz, DMSO-d6) δ 0.85 (d, J =
143.60, 150.73, 156.27, 174.73. Anal. Calcd for C28H29N3O7S 7.0 Hz, CH(CH3)2, 6H), 1.95–2.10 (m, CH(CH3)2, 1H), 3.40 (s,
(551.61): C, 60.97; H, 5.30; N, 7.62%. Found: C, 61.17; H, 5.32; NCH3, 3H), 4.11–4.32 (m, CHFmoc, CH2Fmoc, 3H), 4.49 (app t,
N, 7.64%.
J = 7.8 Hz, α-CH, 1H), 7.24–7.49 (m, Ar-HFmoc, 4H), 7.55–7.70
N-Fmoc-D-phenylalanyl-N-methyl-4-nitrobenzenesulfon- (m, Ar-HFmoc, 2H), 7.79–7.90 (m, Ar-HFmoc, NH, 3H), 8.16 (d,
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amide (5f). Yield: 80%. H NMR (300 MHz, DMSO-d6) δ 2.77 J = 8.7 Hz, Ar-HNs, 2H), 8.36 (d, J = 8.7 Hz, Ar-HNs, 2H). 13C
(dd, J = 9.3 Hz, J = 13.8 Hz, CH2Ph, 1H), 2.98 (dd, J = 5.1 Hz, J = NMR (75 MHz, DMSO-d6) δ 18.26, 19.12, 30.46, 34.12, 47.05,
13.8 Hz, CH2Ph, 1H), 3.30 (s, NCH3, 3H), 3.98–4.32 (m, 59.01, 66.50, 120.65, 124.80, 127.49, 128.05, 129.92, 141.20,
CHFmoc, CH2Fmoc, 3H), 4.77–4.86 (m, α-CH, 1H), 7.06–7.43 (m, 144.15, 144.23, 150.65, 174.11. Anal. Calcd for C27H27N3O7S
Ar-HFmoc, Ar-HPhe, 9H), 7.54–7.66 (m, Ar-HFmoc, 2H), 7.82 (d, (537.58): C, 60.32; H, 5.06; N, 7.82%. Found: C, 60.50; H, 5.08;
J = 7.5 Hz, Ar-HFmoc, 2H), 8.01 (m, NH, 1H), 8.17 (d, J = 8.7 Hz, N, 7.79%.
Ar-HNs, 2H), 8.37 (d, J = 8.7 Hz, Ar-HNs, 2H). 13C NMR
(75 MHz, DMSO-d6) δ 14.54, 21.21, 55.56, 60.20, 79.63, 120.54, (5m). Yield: 89%. 1H NMR (300 MHz, CDCl3) δ 1.49 (d, J = 7.0
N-Fmoc-D-alanyl-N-methyl-4-nitrobenzenesulfonamide
3792 | Org. Biomol. Chem., 2013, 11, 3786–3796
This journal is © The Royal Society of Chemistry 2013