590
S. Azad et al. / Tetrahedron Letters 47 (2006) 587–590
13. Haddad, N.; Wei, X.; Senanayake, C. H.; Xu, J.; Yee, N.
U.S. Patent 2004266767; Chem. Abstr. 2005, 142, 93849.
14. Reviews: (a) Kotsuki, H.; Kumamoto, K. Yuki Gosei
Kagaku Kyokaishi 2005, 63, 770–779; (b) Jenner, G.
Tetrahedron 2005, 61, 3621–3635; (c) High Pressure
Chemistry; van Eldik, R., Kla¨rner, F.-G., Eds.; Wiley-
VCH: Weinheim, 2002; (d) Jenner, G. Tetrahedron 2002,
58, 5185–5202; (e) Kla¨rner, F.-G.; Wurche, F. J. Prakt.
Chem. 2000, 342, 609–636.
15. General procedure: A mixture of Troc-carbamate (1,
1.0 mmol) and amine (2, 1.2 mmol) in THF (ca. 1.5 mL)
was placed in a Teflon reaction vessel, and the mixture was
allowed to react at 0.8 GPa at the appropriate temperature
and for the specified time (Table 1). After the mixture was
cooled and the pressure was released, the mixture was
concentrated in vacuo. The crude product was purified by
silica gel column chromatography (elution with CHCl3–
MeOH) to afford the pure urea 3.
was established by the highly chemoselective transfor-
mation at the Troc group and the easy access to glyco-
conjugated urea derivatives.
Acknowledgements
This work was supported in part by a Grant-in-Aid for
Scientific Research on Priority Areas (17035061) from
MEXT, as well as by a Special Research Grant for
Green Science from Kochi University. K.K. is grateful
for a JSPS research fellowship, for young scientists.
References and notes
1. High-pressure organic chemistry. Part 30. For Part 29, see
Kumamoto, K.; Ichikawa, Y.; Kotsuki, H. Synlett 2005,
2254–2256.
16. Pihuleac, J.; Bauer, L. Synthesis 1989, 61–64.
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1106–1109.
2. Gabriele, B.; Salerno, G.; Mancuso, R.; Costa, M.
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Group Transformations II; Katritzky, A. R., Taylor, R. J.
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19–30.
5. (a) Gante, J. Chem. Ber. 1965, 98, 3334–3339; (b) Izdebski,
J.; Pawlak, D. Synthesis 1989, 423–425; (c) Hutchins, S.
M.; Chapman, K. T. Tetrahedron Lett. 1994, 35, 4055–
4058.
6. Johnston, T. P.; Kussner, C. L.; Carter, R. L.; Frye, J. L.;
Lomax, N. R.; Plowman, J.; Narayanan, V. L. J. Med.
Chem. 1984, 27, 1422–1426.
18. Tilley, J. N.; Sayigh, A. A. R. J. Org. Chem. 1964, 29,
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19. Corrie, J. E. T.; Kirby, G. W.; Sharma, R. P. J. Chem.
Soc., Perkin Trans. 1 1982, 1571–1574.
20. Chien, C.-H.; Leung, M.; Su, J.-K.; Li, G.-H.; Liu, Y.-H.;
Wang, Y. J. Org. Chem. 2004, 69, 1866–1871.
21. pKa values calculated by Advanced Chemistry Develop-
ment (ACD/Labs) Software Solaris V4.67: 2cÆH+ 10.57,
2iÆH+ 5.21; PhNHCOCH3 15.1, C6H13NHCOCH3 16.2.
22. Ichikawa, Y.; Nishiyama, T.; Isobe, M. Tetrahedron 2004,
60, 2621–2627, and references cited therein.
23. Unreacted 5 (35%) was also recovered as an anomeric
mixture (a/b = ca. 10:90). Compound 6 (b-anomer): mp
23
120–122 ꢁC; ½aꢀD ꢁ19.1 (c 0.98, CHCl3); FTIR (KBr) m
1
3322, 1736, 1643, 1577, 1158, 1094, 1069 cmꢁ1; H NMR
7. (a) Thavonekham, B. Synthesis 1997, 1189–1194; (b)
Kitteringham, J.; Shipton, M. R.; Voyle, M. Synth.
Commun. 2000, 30, 1937–1943.
8. Barcelo, G.; Senet, J.-P.; Sennyey, G. Synthesis 1987,
1027–1029.
(400 MHz, CDCl3): d 1.46 (9H, s), 3.36 (1H, t, J =
8.8 Hz), 3.52 (1H, dt, J = 9.3, 3.0 Hz), 3.65–3.75 (4H, m),
3.73 (1H, dd, J = 18.1, 4.9 Hz), 3.88 (1H, dd, J = 18.1,
5.4 Hz), 4.45 (1H, d, JAB = 12.0 Hz), 4.50 (1H, d,
JAB = 11.0 Hz), 4.56 (1H, d, JAB = 12.0 Hz), 4.71 (1H,
d, JAB = 11.5 Hz), 4.79 (1H, d, JAB = 11.5 Hz), 4.79
(1H, d, JAB = 11.0 Hz), 4.87 (1H, d, JAB = 11.0 Hz),
4.87 (1H, t, J = 8.8 Hz), 4.89 (1H, d, JAB = 11.0 Hz),
4.94 (1H, d, J = 8.8 Hz), 5.14 (1H, br), 7.10–7.13 (2H, m),
7.22–7.35 (18H, m); 13C NMR (100 MHz, CDCl3): d 28.0
(·3), 42.7, 68.3, 73.4, 74.6, 74.9, 75.7, 75.9, 77.7, 80.1, 81.4,
81.9, 85.9, 127.6(8) (·2), 127.7(4), 127.8 (·4), 128.0 (·2),
128.1, 128.3 (·2), 128.3(6) (·2), 128.4(2) (·2), 128.6 (·2),
128.7 (·2), 137.8, 137.9, 138.0, 138.4, 156.6, 169.6.
´
´
9. Patonay, T.; Patonay-Peli, E.; Zolnai, L.; Mogyorodi, F.
Synth. Commun. 1996, 26, 4253–4265.
10. For example, see: (a) Kno¨lker, H.-J.; Braxmeier, T.;
Schlechtingen, G. Synlett 1996, 502–504; (b) Lamothe, M.;
Perez, M.; Colovray-Gotteland, V.; Halazy, S. Synlett
1996, 507–508; (c) Chong, P. Y.; Janicki, S. Z.; Petillo, P.
A. J. Org. Chem. 1998, 63, 8515–8521; (d) Matsumura, Y.;
Satoh, Y.; Onomura, O.; Maki, T. J. Org. Chem. 2000, 65,
1549–1551; (e) Gastaldi, S.; Weinreb, S. M.; Stien, D. J.
Org. Chem. 2000, 65, 3239–3240; (f) Shi, M.; Shen, Y.-M.
J. Org. Chem. 2002, 67, 16–21; (g) Li, Q.-F.; Wang, J.-W.;
Dong, W.-S.; Kang, M.-Q.; Wang, X.-K.; Peng, S.-Y. J.
Mol. Cat. A: Chem. 2004, 212, 99–105; (h) Lee, S.-H.;
Matsushita, H.; Clapham, B.; Janda, K. D. Tetrahedron
2004, 60, 3439–3443; (i) Gallou, I.; Eriksson, M.; Zeng, X.;
Senanayake, C.; Farina, V. J. Org. Chem. 2005, 70, 6960–
6963.
11. For our related work on the high-pressure-promoted
uncatalyzed synthesis of thioureas, see: Kumamoto, K.;
Misawa, Y.; Tokita, S.; Kubo, Y.; Kotsuki, H. Tetra-
hedron Lett. 2002, 43, 1035–1038.
12. (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis; Wiley: New York, 1999; (b) Encyclo-
pedia of Reagents for Organic Synthesis; Paquette, L. A.,
Ed.; Wiley: Chichester, 1995; Vol. 7, pp 5068–5069.
23
Compound 6 (a-anomer): colorless gum; ½aꢀD +60.3 (c
0.73, CHCl31); FTIR (KBr) m 3347, 1743, 1650, 1558, 1155,
1072 cmꢁ1; H NMR (400 MHz, CDCl3): d 1.45 (9H, s),
3.61–3.67 (1H, m), 3.70–3.76 (4H, m), 3.77 (1H, dd,
J = 18.1, 5.1 Hz), 3.85 (1H, dd, J = 18.1, 5.9 Hz), 3.93
(1H, dt, J = 10.0, 3.0 Hz), 4.45 (1H, d, JAB = 12.0 Hz),
4.50 (1H, d, JAB = 11.2 Hz), 4.59 (1H, d, JAB = 12.0 Hz),
4.62 (1H, d, JAB = 11.7 Hz), 4.65 (1H, d, JAB = 11.7 Hz),
4.78 (1H, d, JAB = 10.7 Hz), 4.81 (1H, d, JAB = 11.2 Hz),
4.88 (1H, d, JAB = 10.7 Hz), 5.27 (2H, br s), 6.02 (1H, dd,
J = 5.9, 5.1 Hz), 7.14–7.16 (2H, m), 7.24–7.32 (18H, m);
13C NMR (100 MHz, CDCl3): d 28.1 (·3), 42.5, 68.4, 69.8,
72.8, 73.5, 74.9, 75.8, 77.2, 78.0, 78.1, 81.7, 81.9, 127.6(7)
(·3),127.7(2), 127.8(7) (·2), 127.9(5) (·2), 128.1(0) (·2),
128.1(5), 128.3(4) (·2), 128.3(8) (·3), 128.3(9) (·2), 128.6
(·2), 137.1, 137.9, 138.2, 138.3, 158.4, 169.4.