LETTER
Total Synthesis of Sphingofungin F
2987
(15) For recent examples of Wittig and Horner–Wadsworth–
Emmons reaction, see: (a) List, B.; Doehring, A.; Fonseca,
M. T. H.; Job, A.; Torres, R. R. Tetrahedron 2006, 62, 476.
For reviews, see: (b) Harvey, R. G. Curr. Org. Chem. 2004,
8, 303. (c) Quan, L.-G.; Cha, J.-K. Chem. Phys. Lipids 2004,
128. (d) Rein, T.; Vares, L.; Kawasaki, I.; Pedersen, T. M.;
Norrby, P.-O.; Brandt, P.; Tanner, D. Phosphorus, Sulfur
Silicon Relat. Elem. 1999, 144-146, 169.
(16) (a) Cardillo, G.; Simone, A. D.; Gentilucci, L.; Sabatino, P.;
Tomasini, C. Tetrahedron Lett. 1994, 35, 5051. (b) Trost,
B. M.; Dake, G. R. J. Org. Chem. 1997, 62, 5670.
(c) Krawczyk, H. Synth. Commun. 2000, 30, 1787.
(17) Analytical Data of Compound 9.
References and Notes
(1) For reviews, see: (a) Hakomori, S. In Sphingolipid
Biochemistry. Handbook of Lipid Research, Vol. 3; Kafner,
J. N.; Hakomori, S., Eds.; Plenum: New York, 1983, 1.
(b) Merrill, A. H. Jr.; Sweeley, C. C. In Biochemistry of
Lipids, Lipoproteins and Membranes; Vance, D. E.; Vance,
J., Eds.; Elsevier Science B. V.: Amsterdam, 1996, 309.
(c) Hannun, Y. A. Sphingolipid-Mediated Signal
Transduction; Chapman and Hall: New York NY, 1997.
(d) Hannum, Y. A. Science 1996, 274, 1855. (e) Spiegel, S.;
Milstein, S. J. Membr. Biol. 1995, 146, 225. (f) Shayman, J.
A. J. Am. Soc. Nephrol. 1996, 7, 171. (g) Igarashi, Y. J.
Biochem. (Tokyo) 1997, 122, 1080. (h) Ariga, T.; Jarvis, W.
D.; Yu, R. K. J. Lipid. Res. 1998, 39, 1.
Amorphous solid, [a]D25 +15.6 (c 0.35, CHCl3). 1H NMR
(400 MHz, CDCl3): d = 7.67–7.85 (m, 4 H), 7.29 (d, J = 8.2
Hz, 2 H), 6.95 (d, J = 8.4 Hz, 2 H), 4.65 (d, J = 11.0 Hz, 2
H), 4.43 (d, J = 4.1 Hz, 1 H), 4.40 (s, 3 H), 4.28 (m, 1 H),
4.19 (d, J = 10.6 Hz, 1 H), 4.07 (dd, J1 = 10.2 Hz, J2 = 9.0
Hz, 1 H), 3.92 (s, 3 H), 3.65 (dd, J1 = 9.6 Hz, J2 = 8.8 Hz, 1
H), 2.27 (d, J = 7.4 Hz, 2 H), 1.53 (s, 3 H), 1.49 (s, 3 H), 1.39
(s, 3 H), 1.34 (s, 3 H). 13C NMR (100 MHz, CDCl3): d =
171.03, 166.48, 166.50, 159.31, 158.70, 134.57, 134.45,
134.43, 133.63, 131.66, 131.38, 129.89, 129.50, 129.48,
116.45, 110.76, 110.54, 80.02, 79.89, 79.07, 76.75, 75.34,
73.36, 72.16, 71.40, 57.86, 27.33, 27.06, 26.68, 24.65.
HRMS: m/z calcd for C31H35NO10: 581.2261; found:
581.2263.
(2) (a) Hannun, Y. A.; Loomis, C. R.; Merrill, A. H.; Bell, R. M.
J. Biol. Chem. 1986, 261, 2604. (b) Hannun, Y. A. Science
1989, 243, 500.
(3) (a) Nugent, T. C.; Hudlicky, T. J. Org. Chem. 1998, 63, 510.
(b) Kobayashi, S.; Furuta, T.; Hayashi, T.; Nishijima, M.;
Hanada, K. J. Am. Chem. Soc. 1998, 120, 908. (c)Mandala,
S. M.; Harris, G. H. Methods Enzymol. 2000, 311, 335.
(4) (a) VanMiddlesworth, F.; Dufresne, C.; Wincott, F. E.;
Mosley, R. T.; Wilson, K. E. Tetrahedron Lett. 1992, 33,
297. (b) VanMiddlesworth, F.; Giacobbe, R. A.; Lopez, M.;
Garrity, G.; Bland, J. A.; Bartizal, K.; Fromtling, R. A.;
Polishook, J.; Zweerink, M.; Edison, A. M.; Rozdilsky, W.;
Wilson, K. E.; Monaghan, R. L. J. Antibiot. 1992, 45, 861.
(c) Horn, W. S.; Smith, J. L.; Bills, G. F.; Raghoobar, S. L.;
Helms, G. L.; Kurtz, M. B.; Marrinan, J. A.; Frommer, B. R.;
Thornton, R. A.; Mandala, S. M. J. Antibiot. 1992, 45, 1692.
(5) (a) Fujita, T.; Inoue, K.; Yamamoto, S.; Ikumoto, T.; Sasaki,
S.; Toyoma, R.; Yoneta, M.; Hoshino, Y.; Okumoto, T. J.
Antibiot. 1994, 47, 208. (b) Miyake, Y.; Kozutsumi, Y.;
Nakamura, S.; Fujita, T.; Kawasaki, T. Biochem. Biophys.
Res. Commun. 1995, 211, 396. (c) For synthesis of
myriocin, see: Oishi, T.; Ando, K.; Chida, N. Chem.
Commun. 2001, 1932; and references cited therein.
(6) Zweerink, M. M.; Edison, A. M.; Wells, G. B.; Pinto, W.;
Lester, R. L. J. Biol. Chem. 1992, 267, 25032; and references
cited therein.
(7) (a) Trost, B. M.; Lee, C. B. J. Am. Chem. Soc. 2001, 123,
12191. (b) Trost, B. M.; Lee, C. B. J. Am. Chem. Soc. 1998,
120, 6818.
(8) (a) Wang, B.; Yu, X.-M.; Lin, G.-Q. Synlett 2001, 904.
(b) Liu, D.-G.; Wang, B.; Lin, G.-Q. J. Org. Chem. 2000, 65,
9114.
(9) (a) Nakamura, T.; Shiozaki, M. Tetrahedron 2002, 58,
8779. (b) Nakamura, T.; Shiozaki, M. Tetrahedron Lett.
2001, 42, 2701.
(10) Oishi, T.; Ando, K.; Inomiya, K.; Sato, H.; Iida, M.; Chida,
N. Org. Lett. 2002, 4, 151.
(18) (a) Paulsen, H.; Heiker, F. R. Angew Chem., Int. Ed. Engl.
1980, 19, 904. (b) Paulsen, H.; Heiker, F. R. Liebigs Ann.
Chem. 1981, 2180.
(19) Bartlett, P. A.; Johnson, W. S. Tetrahedron Lett. 1970, 4459.
(20) For recent examples of Barton decarboxylation, see:
(a) Masterson, D. S.; Porter, N. A. Org. Lett. 2002, 4, 4253.
(b) Elena, M.; Taddei, M. Tetrahedron Lett. 2001, 42, 3519.
(c) For a review, see: Barton, D. H. R. Aldrichimica Acta
1990, 23, 3.
(21) (a) Gigg, J.; Gigg, R.; Payne, S.; Conant, R. J. Chem. Soc.,
Perkin. Trans. 1 1987, 423. (b) Vacca, J. P.; de Solms, S. J.;
Huff, J. R. J. Am. Chem. Soc. 1987, 109, 3478. (c) Vacca, J.
P.; de Solms, S. J.; Huff, J. R.; Billington, B. C.; Baker, R.;
Kulagowski, J. J.; Mawer, I. M. Tetrahedron 1989, 45, 5679.
(22) Analytical Data of Compound 12.
Amorphous solid, [a]D25 +20.3 (c 0.15, CHCl3). 1H NMR
(400 MHz, CDCl3): d = 7.70–7.88 (m, 4 H), 7.27–7.33 (m, 6
H), 6.86–6.89 (m, 4 H), 6.85 (d, J = 8.3 Hz, 2 H), 4.63–4.68
(m, 6 H), 4.40 (d, J = 3.8 Hz, 1 H), 4.29 (m, 1 H), 3.90 (d,
J = 10.6 Hz, 1 H), 3.83 (2 × s, 6 H), 3.80 (s, 3 H), 3.48 (dd,
J1 = 10.6 Hz, J2 = 10.2 Hz, 1 H), 3.45 (dd, J1 = 10.6 Hz,
J2 = 9.8 Hz, 1 H), 1.67 (s, 3 H), 1.36 (s, 3 H), 1.33 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 166.68, 166.50, 159.31,
159.16, 157.35, 138.56, 138.45, 135.46, 135.15, 134.43,
133.10, 131.58, 131.38, 130.73, 129.89, 129.50, 128.55,
128.38, 128.37, 128.00, 127.99, 113.91, 110.89, 83.22,
81.49, 81.28, 76.50, 75.60, 71.73, 69.19, 55.63, 27.35,
25.91.
(11) (a) Kobayashi, S.; Furuta, T.; Hayashi, T.; Nishijima, M.;
Hanada, K. J. Am. Chem. Soc. 1998, 120, 908.
(b) Kobayashi, S.; Furuta, T. Tetrahedron 1998, 54, 10275.
(12) Lee, K.-Y.; Oh, C.-Y.; Ham, W.-H. Org. Lett. 2001, 4, 4403.
(13) (a) Sano, S.; Kobayashi, Y.; Kondo, T.; Takebayashi, M.;
Maruyama, S.; Fujita, T.; Nagao, Y. Tetrahedron Lett. 1995,
36, 2097. (b) Payette, D. R.; Just, G. Can. J. Chem. 1981, 59,
269.
(23) (a) Bredenkamp, M. W.; Holzapfel, C. W.; Swanepoel, A. D.
Tetrahedron Lett. 1990, 31, 2759. (b) David, S.; Hanessian,
S. Tetrahedron 1985, 41, 643. (c) Pereyre, M.; Quintard, J.-
P.; Rahm, A. Tin in Organic Synthesis; Butterworths:
London, 1987, 261.
(14) The following reference provides detailed procedures for
both the preparation of precursors of both 8 and its
regioisomer, and the preparation of the regioisomer of
compound 8 from the corresponding precursor. It should be
mentioned that the synthesis of 8 was accomplished from its
corresponding precursor following the same procedure. See:
Qiao, L.; Hu, Y.; Nan, F.; Powis, G.; Kozikowski, A. P. Org.
Lett. 2000, 2, 115.
(24) Analytical Data of Compound 6.
Amorphous solid, [a]D25 +8.9 (c 0.20, CHCl3). 1H NMR (400
MHz, CDCl3): d = 7.74–7.90 (m, 4 H), 7.26–7.33 (m, 6 H),
6.86–6.89 (m, 4 H), 6.85 (d, J = 8.0 Hz, 2 H), 5.31 (s, 1 H),
4.64–4.68 (m, 4 H), 4.64 (d, J = 9.6 Hz, 2 H), 3.86 (d, J = 9.2
Hz, 1 H), 3.85 (s, 3 H), 3.81 (s, 3 H), 3.80 (s, 3 H), 3.46 (dd,
J1 = 9.6 Hz, J2 = 7.8 Hz, 1 H), 3.35 (br s, 1 H), 3.35 (s, 3 H),
Synlett 2006, No. 18, 2985–2988 © Thieme Stuttgart · New York