5282
C.-C. Lin et al. / Tetrahedron Letters 44 (2003) 5281–5283
References
1. (a) Kaufer, J. M.; Hakomori, S. In Handbook of Lipids
Research: Sphingolipid Biochemistry; Kanfer, J. N.;
Hakomori, S., Eds.; Plenum Press: New York, 1983; Vol.
3, pp. 1–150; (b) Kolter, T.; Sandhoff, K. Angew. Chem.,
Int. Ed. 1999, 38, 1532–1568.
2. (a) Chang, Y.-T.; Choi, J.; Ding, S.; PrieschI, E. E.;
Baumruker, T.; Lee, J.-M.; Chung, S.-K.; Schultz, P. G.
J. Am. Chem. Soc. 2002, 124, 1856–1857; (b) Turinsky, J.;
Nagel, G. W. Biochem. Biophys. Res. Commun. 1992, 188,
358–364; (c) Dharmawardhane, S.; Rubinstein, B.; Stern,
A. I. Plant Physiol. 1989, 89, 1345–1350; (d) Merrill, A.
H., Jr.; Nimkar, S.; Menaldino, D.; Hannun, Y. A.;
Loomis, C.; Bell, R. M.; Tyagi, J. D.; Lambeth, J. D.;
Stevens, V. L.; Hunter, R.; Liotta, D. C. Biochemistry
1989, 28, 3138–3145; (e) Honda, M.; Ueda, Y.;
Sugiyama, S.; Komori, T. Chem. Pharm. Bull. 1991, 39,
1385–1391; (f) Natori, T.; Morita, M.; Akimoto, K.;
Koezuka, Y. Tetrahedron 1994, 50, 2771–2784.
3. (a) Kolter, T.; Sandhoff, K. Angew. Chem., Int. Ed. 1999,
38, 1532–1568; (b) Koskinen, P. M.; Koskinen, A. M. P.
Synthesis 1998, 1075–1091; (c) Merrill, A. H., Jr.;
Sweeley, C. C. In Biochemistry of Lipids, Lipoproteins and
Membranes; Vance, D. E.; Vance, J. E., Eds.; Elsevier
Science: Amsterdam, 1996; Chapter 12, pp. 309–339.
4. Natori, T.; Morita, M.; Akimoto, K.; Koezuka, Y.;
Agelasphins, Y. Tetrahedron 1994, 50, 2771–2784.
5. Burdin, M.; Kronenberg, M. Curr. Opin. Immunol. 1999,
11, 326–331.
Scheme 1. Synthesis of phytosphingosine from
D-lyxose.
6. (a) Miyamoto, K.; Miyake, S.; Yamamura, T. Nature
2001, 413, 531–534; (b) Kawano, T.; Cui, J.; Koezuka,
Y.; Youra, I.; Kaneko, Y.; Motoki, K.; Ueno, H.; Naka-
gawa, R.; Sato, H.; Kondo, E.; Koseki, H.; Taniguchi,
M. Science 1997, 278, 1626–1629.
7. For recent examples using amino acid precursors, see: (a)
Azuma, H.; Tamagaki, S.; Ogino, K. J. Org. Chem. 2000,
65, 3538–3541; (b) Takikawa, H.; Muto, S.-e.; Mori, K.
Tetrahedron 1998, 54, 3141–3150; (c) Imashiro, R.;
Sakurai, O.; Yamashita, T.; Horikawa, H. Tetrahedron
1998, 54, 10657–10670; (d) Yoda, H.; Oguchi, T.; Tak-
abe, K. Tetrahedron: Asymmetry 1996, 7, 2113–2116; (e)
Dondoni, A.; Fantin, G.; Fogagnolo, M.; Pedrini, P. J.
Org. Chem. 1990, 55, 1439–1446; (f) Sugiyama, S.;
Honda, M.; Komori, T. Liebigs Ann. Chem. 1990, 1069–
1078.
8. For recent examples using sugar precursors, see: (a)
Plettenburg, O.; Bodmer-Narkevitch, V.; Wong, C.-H. J.
Org. Chem. 2002, 67, 4559–4564; (b) Luo, S.-Y.; Thopate,
S. R.; Hsu, C.-Y.; Hung, S.-C. Tetrahedron Lett. 2002,
43, 4889–4892; (c) Graziani, A.; Passacantilli, P.;
Piancatelli, G.; Tani, S. Tetrahedron: Asymmetry 2000,
11, 3921–3937; (d) Figueroa-Pe´rez, S.; Schmidt, R. R.
Carbohydr. Res. 2000, 328, 95–102; (e) Murakami, T.;
Taguchi, K. Tetrahedron 1999, 55, 989–1004; (f) Wee, A.
G. H.; Tang, F. Tetrahedron Lett. 1996, 37, 6677–6680;
(g) Li, Y.-L.; Mao, X.-H.; Wu, Y.-L. J. Chem. Soc.,
Perkin Trans. 1 1995, 1559–1563; (h) Matsumoto, K.;
Ebata, T.; Matsushita, H. Carbohydr. Res. 1995, 279,
93–106.
to remove the acetal and trityl groups and simulta-
neously reduce the azide and double bond of 7 in a
one-pot procedure. Thus, a solution of 7 in CHCl3/
MeOH/HCl(aq) (2/2/1) was treated with a catalytic
amount of Pd(OH)2 under an atmosphere of hydrogen
for 15 h at room temperature to give phytosphingosine
1 in 52% yield.
In conclusion, we have devised a very efficient method
for the synthesis of phytosphingosine by using the
inexpensive starting material
lidene- -lyxofuranose is also the relatively inexpensive
starting material). This method only requires six steps
(from 2,3-O-isopropylidene- -lyxofuranose) to give
D-lyxose (2,3-O-isopropy-
D
D
phytosphingosine in 28% overall yield. To our knowl-
edge, this method is so far the shortest and relatively
high-yielding route for a potential large-scale synthesis
of phytosphingosine. By using different Wittig reagents,
our method can also be modified to prepare a variety of
sphingosine analogs.
Acknowledgements
The authors thank the Academia Sinica, National Sci-
ence Council in Taiwan (NSC 91-3112-P-001-041-Y
and NCS 91-2323-B-001-002), and National Taiwan
University for their financial support.
9. For recent examples using various chiral precursors, see:
(a) Nakamura, T.; Shiozaki, M. Tetrahedron 2001, 57,
9087–9092; (b) He, L.; Byun, H.-S.; Bittman, R. J. Org.
Chem. 2000, 65, 7618–7626; (c) Martin, C.; Pru¨nck, W.;