A Convergent Route for the Total Synthesis of the Eleuthesides

Angewandte Chemie - International Edition

Volumn 37, Issue 1-2, 1998, Pages 185-186

  Chen, Xiao Tao ^a,b   Gutteridge, Clare E ^a   Bhattacharya, Samit K ^a   Zhou, Bishan ^a   Pettus, Thomas R R ^a   Hascall, Tony ^a   Danishefsky, Samuel J ^a  

^a Havemeyer Hall ^*  (United States)

^b MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

Author keywords

Antitumor agents; Cyclophanes; Eleuthesides; Natural products; Total synthesis

Indexed keywords

EID: 0031882649     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19980202)37:1/2<185::aid-anie185>3.0.co;2-l     Document Type: Article

References (25)

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3. a) W. H. Fenical, P. R. Jensen, T. Lindel (UC), US Patent No. 5473057, 1995 [Chem. Abstr. 1996, 102, 194297z]; b) T. Lindel, W. H. Fenical, P. R. Jensen, B. H. Long, A. M. Casazza, J. Carboni, C. R. Fairchild, J. Am. Chem. Soc. 1997, 119, 8744.
4. a) W. H. Fenical, P. R. Jensen, T. Lindel (UC), US Patent No. 5473057, 1995 [Chem. Abstr. 1996, 102, 194297z]; b) T. Lindel, W. H. Fenical, P. R. Jensen, B. H. Long, A. M. Casazza, J. Carboni, C. R. Fairchild, J. Am. Chem. Soc. 1997, 119, 8744.
5. a) M. D'Ambrosio, A. Guerriero, F. Pietra, Helv. Chim. Acta 1987, 70, 2019;
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9. D. T. Hung, T. F. Jamison, S. L. Schreiber. Chem. Biol. 1996, 3, 623.
10. (R)-(-)-α-Phellandrene 4 is available from Fluka Chemical Corp.
11. For preparation see: M. A. Keegstra, A. J. A. Klomp, L. Brandsma, Synth. Commun. 1990, 20, 3371. For use see: U. Wellmar. J. Heterocycl. Chem. 1995, 32, 1159. For 2-iodo-5-(iodomagnesium) furan see: H. Gilman, G. F. Wright, J. Am. Chem. Soc. 1933, 55, 3302. For 2-bromo- 5-lithiothiophene see: M.-J. Shiao, L.-H. Shih, W.-L. Chia, T.-Y. Chau, Heterocvcles 1991, 32, 2111.
12. For preparation see: M. A. Keegstra, A. J. A. Klomp, L. Brandsma, Synth. Commun. 1990, 20, 3371. For use see: U. Wellmar. J. Heterocycl. Chem. 1995, 32, 1159. For 2-iodo-5-(iodomagnesium) furan see: H. Gilman, G. F. Wright, J. Am. Chem. Soc. 1933, 55, 3302. For 2-bromo- 5-lithiothiophene see: M.-J. Shiao, L.-H. Shih, W.-L. Chia, T.-Y. Chau, Heterocvcles 1991, 32, 2111.
13. For preparation see: M. A. Keegstra, A. J. A. Klomp, L. Brandsma, Synth. Commun. 1990, 20, 3371. For use see: U. Wellmar. J. Heterocycl. Chem. 1995, 32, 1159. For 2-iodo-5-(iodomagnesium) furan see: H. Gilman, G. F. Wright, J. Am. Chem. Soc. 1933, 55, 3302. For 2-bromo- 5-lithiothiophene see: M.-J. Shiao, L.-H. Shih, W.-L. Chia, T.-Y. Chau, Heterocvcles 1991, 32, 2111.
14. For preparation see: M. A. Keegstra, A. J. A. Klomp, L. Brandsma, Synth. Commun. 1990, 20, 3371. For use see: U. Wellmar. J. Heterocycl. Chem. 1995, 32, 1159. For 2-iodo-5-(iodomagnesium) furan see: H. Gilman, G. F. Wright, J. Am. Chem. Soc. 1933, 55, 3302. For 2-bromo- 5-lithiothiophene see: M.-J. Shiao, L.-H. Shih, W.-L. Chia, T.-Y. Chau, Heterocvcles 1991, 32, 2111.
15. For a ketene cycloaddition with a cyclohexadiene see the following: a) M. L. Greenlee, J. Am. Chem. Soc. 1981, 103, 2425. For a diaster- eoselective ketene cycloaddition see: A. Kanazawa, P. Delair, M. Pourashraf, A. E. Greene, J. Chem. Soc. Perkin Trans. 1 1997, 1911.
16. For a ketene cycloaddition with a cyclohexadiene see the following: a) M. L. Greenlee, J. Am. Chem. Soc. 1981, 103, 2425. For a diaster- eoselective ketene cycloaddition see: A. Kanazawa, P. Delair, M. Pourashraf, A. E. Greene, J. Chem. Soc. Perkin Trans. 1 1997, 1911.
17. B. M. Trost, M. Preckel, L. M. Leichter. J. Am. Chem. Soc. 1975, 97, 2224.
18. Compound 17a (in contrast to the desired 17) undergoes partial lactonization during workup. This lactone can be converted back to 17a. Epimer 17a can be recycled to the synthetic mainstream by oxidation, followed by reduction of the common ketone. These adjustments to the main synthetic stream will be reported in the full paper.
19. For a review of the Nozaki-Kishi reaction see: P. Cintas, Synthesis 1992, 248. See also: M. Eckhardt, R. Brückner, Liebigs Ann. 1996, 473.
20. For a review of the Nozaki-Kishi reaction see: P. Cintas, Synthesis 1992, 248. See also: M. Eckhardt, R. Brückner, Liebigs Ann. 1996, 473.
21. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC-100974. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ (fax: int. code +(44)1223336-033; e-mail: deposit@ccdc.cam.ac.uk). No claims, regarding absolute stereochemistry, are based on this data.
22. Sarcodictyin and eleutherobin were recently synthesized: K. C. Nicolaou, J.-Y. Xu, S. Kim, T. Ohshima. S. Hosokawa, J. Pfefferkorn, J. Am. Chem. Soc. 1997, 119, 11353; K. C. Nicolaou, F. van Delft, T. Ohshima, D. Vourloumis, J. Xu, S. Hosokawa, J. Pfefferkorn, S. Kim, T. Li, Angew. Chem. 1997, 109, 2630; Angew. Chem. Int. Ed. Engl. 1997, 36, 2520.
23. Sarcodictyin and eleutherobin were recently synthesized: K. C. Nicolaou, J.-Y. Xu, S. Kim, T. Ohshima. S. Hosokawa, J. Pfefferkorn, J. Am. Chem. Soc. 1997, 119, 11353; K. C. Nicolaou, F. van Delft, T. Ohshima, D. Vourloumis, J. Xu, S. Hosokawa, J. Pfefferkorn, S. Kim, T. Li, Angew. Chem. 1997, 109, 2630; Angew. Chem. Int. Ed. Engl. 1997, 36, 2520.
24. Sarcodictyin and eleutherobin were recently synthesized: K. C. Nicolaou, J.-Y. Xu, S. Kim, T. Ohshima. S. Hosokawa, J. Pfefferkorn, J. Am. Chem. Soc. 1997, 119, 11353; K. C. Nicolaou, F. van Delft, T. Ohshima, D. Vourloumis, J. Xu, S. Hosokawa, J. Pfefferkorn, S. Kim, T. Li, Angew. Chem. 1997, 109, 2630; Angew. Chem. Int. Ed. Engl. 1997, 36, 2520.
25. Note added in proof: We have recently completed a synthesis of eleutherobin: X.-T. Chen, B. Zhou, S. K. Bhattacharya, C. E. Gutteridge, T. R. R. Pettus, S. J. Danishefsky, Angew. Chem. and Angew. Chem. Int. Ed., in press.