The total synthesis of eleutherobin: A surprise ending

Angewandte Chemie - International Edition

Volumn 37, Issue 6, 1998, Pages 789-792

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

^a Havemeyer Hall ^*  (United States)

^b MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

Author keywords

Antitumor agents; Eleutherobin; Glycosylations; Stille coupling; Total synthesis

Indexed keywords

EID: 0031924818     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980403)37:6<789::AID-ANIE789>3.0.CO;2-3     Document Type: Article

References (42)

1. For sarcodictyins see: a) M. D'Ambrosio, A. Guerriero, F. Pietra, Helv. Chim. Acta 1987, 70, 2019; b) ibid. 1988, 71, 964.
2. For sarcodictyins see: a) M. D'Ambrosio, A. Guerriero, F. Pietra, Helv. Chim. Acta 1987, 70, 2019; b) ibid. 1988, 71, 964.
3. For eleuthosides see: S. Ketzinel, A. Rudi, M. Schleyer, Y. Benayahu, Y. Kashman, J. Nat. Prod. 1996, 59, 873. Pending development of an official name for this exciting family of natural products, we are referring to them as "eleuthesides" based on eleutherobin as the key member of the grouping.
4. a) W. H. Fenical, P. R. Jensen, T. Lindel, (University of California) US-A 5,473,057, 1995 [Chem. Abstr., 1996, 124, 194297z];
5. 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;
6. c) B. H. Long, C. R. Fairchild, A. J. Wasserman, J. Carboni, A. M. Casazza, W. H. Fenical, Cancer Res., 1997, in press. We thank Professor Fenical for providing us with these papers in advance of publication.
7. a) K. C. Nicolaou, F. van Delft, T. Ohshima, D. Vourloumis, J. -Y. Xu, S. Hosokawa, J. Pfefferkorn, S. Kim, T. Li, Angew. Chem. 1997, 109, 2631: Angew. Chem. Int. Ed. Engl. 1997, 36, 2520.
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10. c) For synthetic studies in the arabinose section of eleutherobin see: K. C. Nicolaou, J. I. Trujillo, K. Chibale, Tetrahedron, 1997, 53, 8751.
11. X. -T. Chen, C. E. Gutteridge, S. K. Bhattacharya, B. Zhou, T. R. R. Pettus, T. Haskall, S. J. Danishefsky, Angew. Chem. 1998, 110, 196; Angew. Chem. Int. Ed. 1998, 37, 185.
12. X. -T. Chen, C. E. Gutteridge, S. K. Bhattacharya, B. Zhou, T. R. R. Pettus, T. Haskall, S. J. Danishefsky, Angew. Chem. 1998, 110, 196; Angew. Chem. Int. Ed. 1998, 37, 185.
13. For use of N-(5-chloro-2-pyridyl)triflimide as a triflating reagent see: a) D. L. Comins, A. Dehghani, Tetrahedron Lett. 1992, 33, 6299; b) D. L. Comins, A. Dehghani, C. J. Foti, S. P. Joseph, Org. Synth. 1996, 74, 77.
14. For use of N-(5-chloro-2-pyridyl)triflimide as a triflating reagent see: a) D. L. Comins, A. Dehghani, Tetrahedron Lett. 1992, 33, 6299; b) D. L. Comins, A. Dehghani, C. J. Foti, S. P. Joseph, Org. Synth. 1996, 74, 77.
15. The data provided in references [2] and [3], pertaining to eleuthoside (A and B) and eleutherobin, respectively, do not rigorously establish the absolute stereochemical nature of the sugar domain. The total synthesis (ref. [4]) did not explicitly deal with the neoeleutherobin issue raised here.
16. By conventions of carbohydrate nomenclature, α and β in the arabinose series correspond to the configurational relationship between C-1 and C-4 of the pyranoside. (For the nomenclature of carbohydrates see: A. D. McNaught Carbohydr. Res. 1997, 197, 1). In terms of the structures presented here, α would correspond to the equatorial anomer and β to the axial one.
17. For an interesting example of metalated [((tetrahydropyran-2-yl)-oxy)methyl] species see: D. K. Hutchinson, P. L. Fuchs, J. Am. Chem. Soc. 1987, 109, 4930.
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27. For selective alkyl transfer to a vinyl iodide using internal coordination at tin see: E. Vedejs, A. R. Haight, W. O. Moss J. Am. Chem. Soc. 1992, 114, 6556.
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30. c) H. Lönn, ibid. 1985, 139, 105, 115.
31. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
32. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
33. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
34. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
35. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
36. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
37. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
38. D. Seebach, N. Meyer Angew. Chem. 1976, 88, 481; Angew. Chem. Int. Ed. Engl. 1976, 15, 438. We also approached the synthesis of the stannyl methyloxy compounds (19, 20 etc.) by a Schmidt-type (R. R. Schmidt, M. Reichrath, Angew. Chem. 1979, 91, 497; Angew. Chem. Int. Ed. Engl. 1979, 18, 466; R. R. Schmidt, ibid. 1986, 98, 213 and 1986, 25, 212) alkylation of the anomeric hydroxyl with tributylstannylmethyl iodide. For preparation of the alkylating agent see: a) S. L. Buchwald, R. B. Nielsen, J. C. Dewan, Organometallics 1989, 8, 1593; b) D. E. Seitz, J. J. Carroll, C. P. Cartaya M. , S-H. Lee, A. Zapata Synth. Commun. 1983, 13, 129.
39. a) See ref. [1 a];
40. b) H. Mawlawi, M. C. Monje, A. Lattes, M. Riviére, J. Heterocycl. Chem. 1992, 29, 1621.
41. [4a]
42. D = + 44.5 (c = 0.09 in MeOH).