S. Jiang et al. / Tetrahedron Letters 47 (2006) 23–25
25
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reaction mixture was diluted with ethyl ether (100 mL)
and washed with 1 N HCl (5 · 100 mL). The organic
layer was washed with brine, dried over Na2SO4, and
evaporated to give a crude oil 5 (1.54 g, 83%). To the
mixture of the above oil, CH3OH (20 mL), and 10%
Pd–C (0.3 g) was stirred vigorously under a H2 atmo-
sphere until hydrogen was absorbed to saturation. The
mixture was filtrated and concentrated to give a crude
oil 6 (1.02 g, 100%). A mixture of the above oil, N-(9-
fluorenylmethoxycarbonyloxy)succinimide (1.43 g, 4.24
mmol) and NaHCO3 (1.43 g, 16.96 mmol) in water
and acetonitrile (1:1, 20 mL) was stirred at room tem-
perature overnight. Acetonitrile was evaporated under
reduced pressure, the resulting solution was adjusted
to pH = 4 using 10% citric acid. The mixture was
extracted with EtOAc. The combined organic layers
were washed with brine, dried over Na2SO4, and
concentrated and purified by flash chromatography
1
to afford 1 as a solid (1.79 g, 96% from 6). H NMR
(400 MHz, CDCl3): 7.76 (2H, d, J = 7.6 Hz), 7.59 (2H,
dd, J = 3.2, 7.2 Hz), 7.40 (2H, dd, J = 7.2 Hz), 7.40
(2H, ddd, J = 1.2, 7.6 Hz), 5.58 (1H, d, J = 8.0 Hz),
4.45 (2H, m), 4.35 (1H, m), 4.22 (1H, t, J = 6.8 Hz),
3.41 (1H, t, J = 7.2 Hz), 2.46 (1H, m), 2.21 (1H, m),
1.46–1.48 (18H, m) ppm. 13C NMR (100 MHz, CDCl3):
175.3, 168.4, 168.2, 156.2, 143.8, 143.6, 141.2, 127.7,
127.1, 125.1, 119.9, 82.4, 82.3, 67.9, 67.3, 52.4, 50.8,
12. Effenberger, F.; Muller, M.; Keller, R.; Wild, W.; Ziegler,
T. J. Org. Chem. 1990, 55, 3064–3067.
13. Attwood, M. R.; Carr, M. G.; Jordan, S. Tetrahedron
Lett. 1990, 31, 283–286.
14. Ho, P. T.; Ngu, K. Pept. Res. 1994, 7, 249–254.
15. Dugave, C.; Menez, A. J. Org. Chem. 1996, 61, 6067–
6070.
16. Tanaka, K. I.; Yoshifuji, S.; Nitta, Y. Chem. Pharm. Bull.
1986, 34, 3879–3884.
17. Schuermann, M. A.; Keverline, K. I.; Hiskey, R. G.
Tetrahedron Lett. 1995, 36, 825–828, and references cited
herein.
18. Boggs, N. T.; Goldsmith, B.; Gawley, R. E.; Koehler,
K. A.; Hiskey, R. G. J. Org. Chem. 1979, 44, 2262–2269.
19. The price of Fmoc-c-carboxy-L-glutamic acid c,c-di-tert-
butyl ester is $900 per gram in 2004–2005 AnaSpec
catalog.
47.0, 30.7, 27.8, 27.7 ppm. IR (film): 3397, 3182, 2978,
25
1723, 1670, 1531, 1150, 1050 cmꢀ1. ½aꢁD ꢀ 8:7 (c 1.0,
MeOH) [lit.25 ꢀ8.6 (c 0.173, MeOH)]. FAB-MS m/z (rel-
ative intensity) 526 (M+H+, 1), 470 (M+H+ꢀt-Bu, 4),
414 (M+H+ꢀ2t-Bu, 31). HRMS (FAB): calcd for
C29H36NO8 [M+H]+ 526.244, found 526.247.
20. Konas, D. W.; Pankuch, J. J.; Coward, J. K. Synthesis.
2002, 17, 2616–2626, and references cited herein.
21. Jiang, S.; Liu, Z.-H.; Sheng, G.; Zeng, B. B.; Chen, X.-G.;
Wu, Y.-L.; Yao, Z.-J. J. Org. Chem. 2002, 67, 3404–
3408.
22. Jiang, S.; Li, Y.; Chen, X.-G.; Hu, T.-S.; Wu, Y.-L.; Yao,
Z.-J. Angew. Chem., Int. Ed. 2004, 43, 329–334.
23. Cong, X.; Hu, F.; Liu, K.-G.; Liao, Q.-J.; Yao, Z.-J.
J. Org. Chem. 2005, 70, 4514–4516.
Acknowledgements
This research was supported by the Intramural Research
Program of the NIH, National Cancer Institute, Center
for Cancer Research. We are grateful to Dr. Krzysztof
Krajewski, for advice, helpful discussions, and a critical
reading of the manuscript.
24. Vedejs, E.; Dent, W. H.; Gapinski, D. M.; McClure, C. K.
J. Am. Chem. Soc. 1987, 109, 5437–5446.
References and notes
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