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Bioscience, Biotechnology, and Biochemistry Volume 62, 1998 - Issue 12
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Original Articles

Simple Synthesis of Both Enantiomers of the C7-C12 Segment of Epothilones

Shinji TANIMORIDepartment of Applied Biochemistry, College of Agriculture, Osaka Prefecture University
,
Koichi TANIMOTODepartment of Applied Biochemistry, College of Agriculture, Osaka Prefecture University
&
Mitsunori KIRIHATADepartment of Applied Biochemistry, College of Agriculture, Osaka Prefecture University
Pages 2428-2430 | Received 10 Jun 1998, Accepted 05 Aug 1998, Published online: 22 May 2014

  • 1) Höfle, G., Bedorf, N., Steinmetz, H., Schomburg, D., Gerth, K., and Reichenbach, H., Epothilone A and B-novel 16-membered macrolides with cytotoxic activity: isolation, crystal structure, and conformation in solution. Angew. Chem. Int. Ed. Engl., 35, 1567-1569 (1996).
  • 2) Bollag, D. M., McQueney, P. A., Zhu, J., Hensens. O., Koupal, L., Liesch, J., Goetz, M., Lazarides, E., and Woods, C. M., Epothilones, a new class of microtubule-stabilizing agents with taxol-like mechanism of action. Cancer Res., 55, 2325-2333 (1995).
  • 3) Total syntheses: (a) Nicolaou, K. C., He, Y., Vourloumis, D., Vallberg, H., Roschangar, F., Sarabia, S., Ninkovic, S., Yang, Z., and Trujillo, J. I., The olefin metathesis approach to epothilone A and its analogues. J. Am. Chem. Soc., 119, 7960-7973 (1997).
  • 3) (b) Nicolaou, K. C., Ninkovic, S., Sarabia, F., Vourloumis, D., He, Y., Vallberg, H., Finlay, M. R. V., and Yang, Z., Total syntheses of epothilones A and B via a macrolactonization-based strategy. J. Am. Chem. Soc., 119, 7974-7991 (1997).
  • 3) (c) Meng, D., Bertinato, P., Balog, A., Su, D.-S., Kamenecka, T., Sorensen, E. J., and Danishefsky, S. J., Total syntheses of epothilones A and B. J. Am. Chem. Soc., 119, 10073-10092 (1997).
  • 3) (d) Nicolaou, K. C., Winssinger, N., Pastor, J., Ninkovic, S., Sarabia, F., He, Y., Vourloumis, D., Yang, Z., Li, T., Giannakakou, P., and Hamel, E., Synthesis of epothilones A and B in solid and solution phase. Nature, 387, 268-272 (1997).
  • 3) (e) Schinzer, D., Limberg, A., Bauer, A., Böhm, O. M., and Cordes, M., Total synthesis of (-)-epothilone A. Angew. Chem. Int. Ed. Engl., 36, 523-524 (1997).
  • 4) Analog syntheses: (a) Balog, A., Bertinato, P., Su, D.-S., Meng, D., Sorensen, E., Danishefsky, S. J., Zheng, Y.-H., Chou, T.-C., He, L., and Horwitz, S. B., Stereoselective synthesis and evaluation of compounds in the 8-desmethylepothilone A series: some surprising observations regarding their chemical and biological properties. Tetrahedron Lett., 38, 4529-4532 (1997).
  • 4) (b) Meng, D., Su, D.-S., Balog, A., Bertinato, P., Sorensen, E. J., Danishefsky, S. J., Zheng, Y.-H., Chou, T.-C., He, L., and Horwitz, S. B., Remote effects in macrolide formation through ring-forming olefin metathesis: an application to the synthesis of fully active epothilone congeners. J. Am. Chem. Soc., 119, 2733-2734 (1997).
  • 4) (c) Nicolaou, K. C., Sarabia, F., Ninkovic, S., Finlay, M. R. V., and Boddy, C. N. C., Probing the ring size of epothilones: total synthesis of [14]-, [15]-, [17]-, and [18]epothilone A. Angew. Chem. Int. Ed. Engl., 37, 81-84 (1998).
  • 4) (d) Nicolaou, K. C., He, Y. Roschangar, F., King, K. P., Vourloumis, D., and Li, T., Total synthesis of epothilone E and analogues with modified side chains through the Stille coupling reaction. Angew. Chem. Int. Ed. Engl., 37, 84-87 (1998).
  • 5) Partial syntheses: (a) Schinzer, D., Limberg, A., and Böhm, O. M., Studies towards the total synthesis of epothilones: asymmetric synthesis of key fragments. Chem. Eur. J., 2, 1477-1482 (1996).
  • 5) (b) Nicolaou, K. C., He, Y., Vourloumis, D., Vallberg, H., and Yang, Z., An approach to epothilones based on olefin metathesis. Angew. Chem. Int. Ed. Engl., 35, 2399-2401 (1996).
  • 5) (c) Mulzer, J., and Mantoulidis, A., Synthesis of the C(1)-C(9) segment of the cytotoxic macrolides epothilone A and B. Tetrahedron Lett., 37, 9179-9182 (1996).
  • 5) (d) Claus, E., Pahl, A., Jones, P. G., Meyer, H. M., and Kalesse, M., Synthesis of the C1-C9 segment of epothilones. Tetrahedron Lett., 38, 1359-1362 (1997).
  • 5) (e) Gabriel, T. and Wessjohann, L., The chromium-Reformatsky reaction: asymmetric synthesis of the aldol fragment of the cytotoxic epothilones from 3-(2-bromoacyl)-2-oxazolidinones. Tetrahedron Lett., 38, 1363-1366 (1997).
  • 5) (f) Taylor, R. E., and Haley, J. D., Towards the synthesis of epothilone A: enantioselective preparation of the thiazole side chain and macrocyclic ring closure. Tetrahedron Lett., 38, 2061-2064 (1997).
  • 5) (g) Mulzer, J., Mantoulidis, A., and Öhler, E., Synthesis of the C(11)-C(20) segment of cytotoxic macrolide epothilone B. Tetrahedron Lett., 38, 7725-7728 (1997).
  • 5) (h) Chakraborty, T. K., and Dutta, S., Radical-induced opening of trisubstituted epoxides: application in the synthesis of C1-C12 segment of epothilones. Tetrahedron Lett., 39, 101-104 (1998).
  • 5) (i) Bijoy, P., and Avery, M. A., Synthetic studies directed torwards epothilone A: enantioselective synthesis of a C7-C15 carboxaldehyde segment. Tetrahedron Lett., 39, 209-212 (1998).
  • 6) Both enantiomers of the hydroxy ester (5 and 6) are available from Tokyo Chemical Industry (TCI) Co. Ltd. and have been frequently used as chiral building blocks for the synthesis of natural products. Recent examples are in the following review: Norcross, R. D., and Paterson, I., Total synthesis of bioactive marine macrolides. Chem. Rev., 95, 2041-2114 (1995).
  • 7) O’Connor, S. J., and Williard, P. G., Strategy for the synthesis of the C10-C19 portion of amphidinolide-A. Tetrahedron Lett., 30, 4637-4640 (1989).
  • 8) Lipshuts, B. H., in Organometallics in Synthesis, ed. Schlosser, M., pp. 283-382, Wiley, New York, 1994; Kotsuki, H., Kadota, I., and Ochi, M., A novel carbon-carbon bond-forming reaction of triflates with copper (I)-catalyzed Grignard reagents: a new concise and enantiospecific synthesis of (+)-exo-brevicomin, (5R, 6S)-(-)-6-acetoxy-5-hexadecanolide, and L-factor. J. Org. Chem., 55, 4417-4422 (1990).
  • 9) The triflate corresponding to 8 was too unstable for use in the reaction.

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