A concise synthesis of (-)-hispidospermidin guided by a postulated biogenesis [10]

Journal of the American Chemical Society

Volumn 122, Issue 39, 2000, Pages 9556-9557

  Tamiya, Junko ^a   Sorensen, Erik J ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,2 DICARBONYL DERIVATIVE; ALKENE DERIVATIVE; HALOGENATED HYDROCARBON; RUTHENIUM;

CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; LETTER; OXIDATION;

EID: 0034605427     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0026758     Document Type: Letter

References (26)

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3. For total syntheses of hispidospermidin, see: (a) Frontier, A. J.; Raghavan, S.; Danishefsky, S. J. J. Am. Chem. Soc. 1997, 119, 6686. (b) Overman, L. E.; Tomasi, A. L. J. Am. Chem. Soc. 1998, 120, 4039. (c) Frontier, A. J.; Raghavan, S.; Danishefsky, S. J. J. Am. Chem. Soc. 2000, 122, 6151.
4. For total syntheses of hispidospermidin, see: (a) Frontier, A. J.; Raghavan, S.; Danishefsky, S. J. J. Am. Chem. Soc. 1997, 119, 6686. (b) Overman, L. E.; Tomasi, A. L. J. Am. Chem. Soc. 1998, 120, 4039. (c) Frontier, A. J.; Raghavan, S.; Danishefsky, S. J. J. Am. Chem. Soc. 2000, 122, 6151.
5. For total syntheses of hispidospermidin, see: (a) Frontier, A. J.; Raghavan, S.; Danishefsky, S. J. J. Am. Chem. Soc. 1997, 119, 6686. (b) Overman, L. E.; Tomasi, A. L. J. Am. Chem. Soc. 1998, 120, 4039. (c) Frontier, A. J.; Raghavan, S.; Danishefsky, S. J. J. Am. Chem. Soc. 2000, 122, 6151.
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7. Cyclization of trans,trans-farnesyl pyrophosphate (1) to γ-bisabolene (2) presupposes an initial isomerization of 1 to nerolidyl pyrophosphate or alternatively to cis,trans-farnesyl pyrophosphate. For discussions, see: (a) Cane, D. E. Acc. Chem. Res. 1985, 18, 220. (b) Andersen, N. H.; Syrdal, D. D. Tetrahedron Lett. 1972, 2455.
8. Cyclization of trans,trans-farnesyl pyrophosphate (1) to γ-bisabolene (2) presupposes an initial isomerization of 1 to nerolidyl pyrophosphate or alternatively to cis,trans-farnesyl pyrophosphate. For discussions, see: (a) Cane, D. E. Acc. Chem. Res. 1985, 18, 220. (b) Andersen, N. H.; Syrdal, D. D. Tetrahedron Lett. 1972, 2455.
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10. The biosynthesis of (-)-hispidospermidin has not yet been described.
11. We achieved a 5-step synthesis of ketone 6 from (R)-(+)-pulegone (5) and isoprene by a modification of the 7-step sequence described by Marx and Norman (see: J. Org. Chem. 1975, 40, 1602).
12. 8-Phenylmenthyl pyruvate (7) was prepared by the reaction of (-)-8-phenylmenthol with pyruvic acid in the presence of p-toluenesulfonic acid in refluxing benzene. For a convenient synthesis of 8-phenylmenthol from pulegone, see: (a) Corey, E. J.; Ensley, H. E. J. Am. Chem. Soc. 1975, 97, 6908. (b) Ort, O. Organic Syntheses: John Wiley & Sons: New York, 1993; Collect. Vol. 8, p 522.
13. 8-Phenylmenthyl pyruvate (7) was prepared by the reaction of (-)-8- phenylmenthol with pyruvic acid in the presence of p-toluenesulfonic acid in refluxing benzene. For a convenient synthesis of 8-phenylmenthol from pulegone, see: (a) Corey, E. J.; Ensley, H. E. J. Am. Chem. Soc. 1975, 97, 6908. (b) Ort, O. Organic Syntheses: John Wiley & Sons: New York, 1993; Collect. Vol. 8, p 522.
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15. (b) Chamberlin, A. R.; Bloom, S. H. Org. React. (N.Y.) 1991, 39, 1.
16. For diastereoselective additions of Grignard reagents to the pyruvate ester of (-)-8-phenylmenthol, see: (a) Whitesell, J. K.; Deyo, D.; Bhattacharya, A. J. Chem. Soc., Chem. Commun. 1983, 802. (b) Whitesell, J. K.; Buchanan, C. M. J. Org. Chem. 1986, 51, 5443.
17. For diastereoselective additions of Grignard reagents to the pyruvate ester of (-)-8-phenylmenthol, see: (a) Whitesell, J. K.; Deyo, D.; Bhattacharya, A. J. Chem. Soc., Chem. Commun. 1983, 802. (b) Whitesell, J. K.; Buchanan, C. M. J. Org. Chem. 1986, 51, 5443.
18. We isolated a single tertiary alcohol diastereomer and tentatively assigned its stereochemistry as shown in 9 by analogy to the stereochemical outcomes reported by Whitesell et al. (see refs 11a,b).
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22. (b) For a review of carbonyl ene and Prins reactions, see: Snider, B. B. In Comprehensive Organic Syntheses: Additions to C-X p-Bonds, Part 2; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 2, Chapter 2.1, p 527.
23. We could not isolate the anticipated carbonyl ene product, although it may be a transient intermediate in this process. This transformation even occurs to some extent on silica gel. We do not yet know if the outcome of this reaction is dependent on the identity of the protecting group in 11.
24. Thompson, H. W.; Wong, J. K. J. Org. Chem. 1985, 50, 4270.
25. 2 chromatography or HPLC.
26. Ganem, B.; Osby, J. O. Chem. Rev. 1986, 86, 763.