Synthesis of the macrolide core of migrastatin

Tetrahedron Letters

Volumn 43, Issue 50, 2002, Pages 9039-9042

  Gaul, Christoph ^a   Danishefsky, Samuel J ^a,b  

^a MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

^b Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

LACDAC; Migrastatin; Natural product macrolide; Ring closing metathesis; Tumor cell migration

Indexed keywords

LEWIS ACID; MACROLIDE; MIGRASTATIN; UNCLASSIFIED DRUG;

ACYLATION; ANTINEOPLASTIC ACTIVITY; ARTICLE; CATALYST; CHELATION; CRYSTAL STRUCTURE; DRUG SYNTHESIS; POLYMERIZATION; RING CLOSING METATHESIS;

EID: 0037049195     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(02)02281-5     Document Type: Article

References (21)

1. Nakae K., Yoshimoto Y., Sawa T., Homma Y., Hamada M., Takeuchi T., Imoto M. J. Antibiot. 53:2000;1130-1136.
2. Nakae K., Yoshimoto Y., Ueda M., Sawa T., Takahashi Y., Naganawa H., Takeuchi T., Imoto M. J. Antibiot. 53:2000;1228-1230.
3. Woo E.J., Starks C.M., Carney J.R., Arslanian R., Cadapan L., Zavala S., Licari P. J. Antibiot. 55:2002;141-146.
4. Takemoto Y., Nakae K., Kawatani M., Takahashi Y., Naganawa H., Imoto M. J. Antibiot. 54:2001;1104-1107.
5. Nakamura H., Takahashi Y., Naganawa H., Nakae K., Imoto M., Shiro M., Matsumura K., Watanabe H., Kitahara T. J. Antibiot. 55:2002;442-444.
6. (S)-3-Benzyloxy-1,2-propanediol 2 is commercially available (Fluka, Aldrich), but only at a high cost. Compound 2 can be easily prepared from inexpensive starting materials. See: (a) Kitaori, K.; Furukawa, Y.; Yoshimoto, H.; Otera, J. Tetrahedron 1999, 55, 14381-14390; (b) Xiang, G.; McLaughlin, L. W. Tetrahedron 1998, 54, 375-392.
7. (S)-3-Benzyloxy-1,2-propanediol 2 is commercially available (Fluka, Aldrich), but only at a high cost. Compound 2 can be easily prepared from inexpensive starting materials. See: (a) Kitaori, K.; Furukawa, Y.; Yoshimoto, H.; Otera, J. Tetrahedron 1999, 55, 14381-14390; (b) Xiang, G.; McLaughlin, L. W. Tetrahedron 1998, 54, 375-392.
8. Reetz M.T., Kessler K. J. Org. Chem. 50:1985;5434-5436.
9. The TBDPS group actually serves a dual purpose: It does not only prevent competing β-chelation, but is also a protecting group that is sufficiently stable toward acidic hydrolysis (see the use of CSA in the following transformations).
10. For chelation-controlled cyclocondensations of α-alkoxy aldehydes with synergistically activated dienes, see: Danishefsky S.J., Pearson W.H., Harvey D.F., Maring C.J., Springer J.P. J. Am. Chem. Soc. 107:1985;1256-1268.
11. Luche J.L., Gemal A.L. J. Am. Chem. Soc. 101:1979;5848-5849.
12. Ferrier R.J. J. Chem. Soc. 1964;5443-5449.
13. Crystallographic data (excluding structural factors) for compound 8 have been deposited with the Cambridge Crystallographic Data Centre (CCDC) as deposition no. CCDC 195014.
14. The reaction sequence described in Scheme 2 was actually conducted starting from compound ent-8. For our early studies toward the total synthesis of migrastatin it was more convenient to commence the synthesis with the known aldehyde ent-4 (prepared from D-mannitol: Nicolaou, K. C.; Piscopio, A. D.; Bertinato, P.; Chakraborty, T. K.; Minowa, N.; Koide, K. Chem. Eur. J. 1995, 1, 318-333), leading to diol ent-8. Later, we addressed this problem and developed an efficient synthesis of aldehyde 4 (see Scheme 1).
15. Katzenellenbogen J.A., Crumrine A.L. J. Am. Chem. Soc. 98:1976;4925-4935.
16. Ahmar M., Duyck C., Fleming I. J. Chem. Soc., Perkin Trans. 1. 1998;2721-2732.
17. Tebbe F.N., Parshall G.W., Reddy G.S. J. Am. Chem. Soc. 100:1978;3611-3613.
18. Scholl M., Ding S., Lee C.W., Grubbs R.H. Org. Lett. 1:1999;953-956.
19. For one of the early applications of RCM in complex natural product synthesis, see: Xu Z., Johannes C.W., Salman S.S., Hoveyda A.H. J. Am. Chem. Soc. 118:1996;10926-10927.
20. Yamamoto, K.; Biswas, K.; Gaul, C.; Danishefsky, S. J., manuscript in preparation.
21. +).