4298
J. S. Choi et al. / Tetrahedron Letters 43 (2002) 4295–4299
and Y.L.) is gratefully acknowledged. We are grateful
for the instrumental support from the equipment facil-
ity of CRM-KOSEF, Korea University.
M. E.; Iguchi, S.; Ionescu, D.; El-Faham, A.; Reimer, C.;
Warrass, R. J. Org. Chem. 1999, 64, 4324–4338.
8. Nsc-Py-OH 1a. TLC (EtOAc:hexane=3:1) Rf=0.30; 1H
NMR (300 MHz, DMSO-d6) l 12.15 (brs, 1H), 9.03 (brs,
1H), 8.40 (d, J=8.7 Hz, 2H), 8.17 (d, J=8.7, 2H), 6.88
(s, 1H), 6.50 (s, 1H), 4.34 (t, J=5.4, 2H), 3.89 (t, J=5.6,
2H), 3.76 (s, 3H); 13C NMR (75 MHz, DMSO-d6) l
161.59, 152.13, 150.16, 144.59, 129.27, 124.48, 121.79,
119.78, 118.69, 107.46, 57.59, 54.28, 36.12; HRMS (FAB+)
for C15H15N3O8S (M+), calcd 397.0580, found 397.0582.
Nsc-Im-OH 1b. TLC (EtOAc:MeOH:H2O=25:5:4) Rf=
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1
0.40; H NMR (300 MHz, DMSO-d6) l 9.77 (brs, 1H),
8.37 (d, J=7.8, 2H), 8.16 (d, J=8.4, 2H), 7.15 (s, 1H),
4.37 (brs, 2H), 3.91 (brs, 2H), 3.86 (s, 3H); 13C NMR (75
MHz, DMSO-d6)
l 159.64, 152.16, 150.09, 144.55,
136.86, 131.74, 129.27, 124.45, 113.30, 57.91, 54.20, 35.48;
LRMS (FAB+) for C14H15N4O8S (MH+), calcd 399.1,
found 399.0.
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11. The amount of intact Nsc-Py-OH 1a (0.1 M) after treat-
ment with NH2-Gly-OEt·HCl (0.2 M) and DIEA (0.3 M)
in DMF was determined by analytical HPLC on a C18
column at 254 and 268 nm. tBoc-Py-OH (0.1 M) was
added as an internal standard. Fmoc-Py-OH was selected
as a substrate for comparision experiments.4a Cleavage of
the Fmoc group was performed as described above, with
the exception of monitoring the absorbance at 254 and
290 nm.
12. The deprotection rate was slightly faster by addition of
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (1% v/v) to a
20% piperidine–DMF solution.
13. Piperidine adduct 9. TLC (EtOAc:hexane=3:1) Rf=0.39;
1H NMR (300 MHz, CDCl3) l 8.40 (d, J=8.7, 2H), 8.14
(d, J=9.0, 2H), 3.36 (t, J=6.9, 2H), 2.75 (t, J=6.8, 2H),
2.26 (brs, 4H), 1.33 (brs, 6H); 13C NMR (75 MHz,
CDCl3) l 150.60, 145.73, 129.62, 124.12, 54.01, 53.56,
51.95, 25.52, 23.79; HRMS (FAB+) for C13H19N2O4S
(MH+), calcd 299.1066, found 299.1076; UV (DMF)
umax=267 nm (m=4.7×103).
14. (a) Carpino, L. A.; El-Faham, A. J. Am. Chem. Soc.
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15. Nsc-PyPy-OMe 11. TLC (EtOAc:hexane=3:1) Rf=0.22;
1H NMR (300 MHz, DMSO-d6) l 9.87 (brs, 1H), 9.20
(brs, 1H), 8.43 (d, J=7.5, 2H), 8.19 (d, J=7.5, 2H), 7.46
(s, 1H), 6.89 (s, 1H), 6.81 (s, 1H), 6.77 (s, 1H), 4.37 (brs,
2H), 3.90 (brs, 2H), 3.83 (s, 3H), 3.80 (s, 3H), 3.74 (s,
3H); 13C NMR (75 MHz, DMSO-d6) l 160.81, 158.28,
152.52, 150.43, 144.74, 129.47, 124.67, 122.90, 122.76,
121.56, 120.76, 118.48, 117.36, 108.32, 103.85, 57.49,
54.29, 50.98, 36.19, 36.12.
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17. Ac-PyPyPy-b-Dp 12 and XPyPy-g-PyPyPy-b-Dp 13. The
polyamides 12 and 13 were synthesized on Fmoc-b-Ala-
Wang resin (60 mmol) in a stepwise fashion by a manual
solid-phase method as described.19 Nsc-Py-OH (150
7. (a) Carpino, L. A.; Philbin, M.; Ismail, M.; Truran, G.
A.; Mansour, E. M. E.; Iguchi, S.; Ionescu, D.; El-
Faham, A.; Riemer, C.; Warrass, R.; Weiss, M. S. J. Am.
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