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1993, 34, 5591; (b) Natori, T.; Morita, M.; Akimoto, K.;
Koezuka, Y. Tetrahedron 1994, 50, 2771.
Through the construction of an unsaturated analog of
the fatty acid cerotic acid it was possible to synthesize
protected glycolipid 13, which provided homogeneous
3H8-a-GalCer upon reduction with tritium gas over pal-
ladium black. As a result of the high specific activity
5. Zheng, Z.-H.; Castano, A. R.; Segelke, B. W.; Stura, E.
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A.; Peterson, P. A.; Wilson, I. A. Science 1997, 277,
339.
3
(200 Ci/mmol) obtained, H8-a-GalCer (14) will enable
6. (a) Sakai, T.; Ehara, H.; Koezuka, Y. Org. Lett. 1999, 1,
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Savage, P. B. Org. Lett. 2002, 4, 1267.
facile quantitation of interactions with this glycolipid
or with glycolipid-loaded CD1d complexes to study
in vivo a-GalCer pharmacokinetic properties, on which
we will report in due course.
Acknowledgements
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This work was financially supported by NIH (H.L.P.) the
Netherlands Organization for Scientific Research (H.O.),
the Koninklijke Hollandse Maatschappij der Wetensc-
happen (M.D.P.R. and C.R.B.) and by the Stichting
Fonds Doctor Catharine van Tussenbroek (C.R.B.).
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12. Spectroscopic data for compound 13: H NMR (CDCl3,
References and notes
1
1. For recent reviews on CD1 see: (a) Sugita, M.; Cernadas,
M.; Brenner, M. B. Curr. Opin. Immunol. 2004, 16, 90; (b)
Brigl, M.; Brenner, M. B. Annu. Rev. Immunol. 2004, 22,
817; (c) Watts, C. Nat. Immunol. 2004, 5, 685; (d) Moody,
D. B.; Porcelli, S. A. Nat. Rev. Immunol. 2003, 3, 11.
2. Morita, M.; Motoki, K.; Akimoto, K.; Natori, T.; Sakai,
T.; Sawa, E.; Yamaji, K.; Koezuka, Y.; Kobayashi, E.;
Fukushima, H. J. Med. Chem. 1995, 38, 2176.
500 MHz) d: 7.46–7.28 (m, 25H); 5.93 (d, 1H, J = 16.5 Hz
NH); 5.51 (s, 1H PhCH); 5.00 (d, 1H, J = 3.0 Hz); 4.96–
4.53 (m, 13H); 4.27–3.58 (m, 17H); 2.23–1.90 (m, 3H),
1.70–1.30 (m, 52H); 0.94 (m, 6H). 13C NMR (CDCl3
125 MHz) d: 173.2; 138.8; 138.7; 138.1; 129.1; 128.7; 128.7;
128.6; 128.4; 128.1; 128.0; 127.8; 126.6; 101.3; 100.0;
80.7; 80.2; 79.8; 77.3; 76.0; 74.7; 74.1; 73.6; 72.2; 72.0; 69.7;
68.5; 63.2; 50.6; 37.0; 32.2; 30.6; 30.1; 30.0; 29.7; 29.6;
29.5; 29.2; 29.2; 28.7; 28.5; 26.1; 26.0; 23.0; 19.0; 18.9; 18.6;
14.4.
3. Kawano, T.; Cui, J.; Koezuka, Y.; Toura, I.; Kaneko, Y.;
Motoki, K.; Ueno, H.; Nakagawa, R.; Sato, H.; Kondo,
E.; Koseki, H.; Taniguchi, M. Science 1997, 278, 1626.