The synthesis of (±)-heliotridane and (6S,7S)-dihydroxyheliotridane via sequential hydrogen atom abstraction and cyclisation

Tetrahedron Letters

Volumn 37, Issue 32, 1996, Pages 5825-5828

  Robertson, Jeremy ^a   Peplow, Mark A ^a   Pillai, Jayasheela ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

HELIOTRIDANE; PYRROLIZIDINE ALKALOID; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030570852     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01237-3     Document Type: Article

References (30)

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5. 4. Hydrogen atom transfer and cyclisation: Curran, D. P.; Kim, D.; Liu, H. T.; Shen, W., J. Am. Chem. Soc., 1988, 110, 5900-5902. Early use in pyrrolizidine synthesis: Lathbury, D. C.; Parsons, P. J.; Pinto, I., J. Chem. Soc., Chem. Commun., 1988, 81-82. For an example of the intermolecular trapping of an α-amino radical produced by 1,5-hydrogen atom transfer see: Williams, L.; Booth, S. E.; Undheim, K., Tetrahedron, 1994, 50, 13697-13708.
6. 4. Hydrogen atom transfer and cyclisation: Curran, D. P.; Kim, D.; Liu, H. T.; Shen, W., J. Am. Chem. Soc., 1988, 110, 5900-5902. Early use in pyrrolizidine synthesis: Lathbury, D. C.; Parsons, P. J.; Pinto, I., J. Chem. Soc., Chem. Commun., 1988, 81-82. For an example of the intermolecular trapping of an α-amino radical produced by 1,5-hydrogen atom transfer see: Williams, L.; Booth, S. E.; Undheim, K., Tetrahedron, 1994, 50, 13697-13708.
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8. 6. Motherwell, W. B.; Crich, D., Free Radical Chain Reactions in Organic Synthesis; Academic Press, 1991; pp. 21-22.
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12. 10. Pandey, G.; Reddy, G. R.; Chakrabarti, D., J. Chem. Soc., Perkin Trans. I, 1996, 219-224; Pandey, G.; Chakrabarti, D., Tetrahedron Lett., 1996, 37, 2285-2288; Pandey, G.; Reddy, G. R., Tetrahedron Lett., 1992, 33, 6533-6536.
13. 10. Pandey, G.; Reddy, G. R.; Chakrabarti, D., J. Chem. Soc., Perkin Trans. I, 1996, 219-224; Pandey, G.; Chakrabarti, D., Tetrahedron Lett., 1996, 37, 2285-2288; Pandey, G.; Reddy, G. R., Tetrahedron Lett., 1992, 33, 6533-6536.
14. 10. Pandey, G.; Reddy, G. R.; Chakrabarti, D., J. Chem. Soc., Perkin Trans. I, 1996, 219-224; Pandey, G.; Chakrabarti, D., Tetrahedron Lett., 1996, 37, 2285-2288; Pandey, G.; Reddy, G. R., Tetrahedron Lett., 1992, 33, 6533-6536.
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17. 12. Beckwith, A. L. J.; Lawrence, T.; Serelis, A., J. Chem. Soc., Chem. Commun., 1980, 484-485; Beckwith, A. L. J., Tetrahedron, 1981, 37, 3073-3100; Rajanbabu, T. V., Acc. Chem. Res., 1991, 24, 139-145.
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20. 14. Our own explanation of this stereochemical result will be presented in a forthcoming full paper.
21. 15. Pyrrolizine numbering has been used throughout.
22. 16. Structure 10 has been shown to be the unnatural enantiomer: Cordero, F. M.; Cicchi, S.; Goti, A.; Brandi, A., Tetrahedron Lett., 1994, 35, 949-952; Gurjar, M. K.; Ghosh, L.; Syamala, M.; Jayasree, V., Tetrahedron Lett., 1994, 35, 8871-8872. The natural product (the (-)-isomer) is therefore ent-10 at variance with the original report: Pastuszak, I.; Molyneux, R.; James, L. F.; Elbein, A. D., Biochemistry, 1990, 29, 1886-1891; Molyneux, R., J. Nat. Prod., 1990, 53, 609-614.
23. 16. Structure 10 has been shown to be the unnatural enantiomer: Cordero, F. M.; Cicchi, S.; Goti, A.; Brandi, A., Tetrahedron Lett., 1994, 35, 949-952; Gurjar, M. K.; Ghosh, L.; Syamala, M.; Jayasree, V., Tetrahedron Lett., 1994, 35, 8871-8872. The natural product (the (-)-isomer) is therefore ent-10 at variance with the original report: Pastuszak, I.; Molyneux, R.; James, L. F.; Elbein, A. D., Biochemistry, 1990, 29, 1886-1891; Molyneux, R., J. Nat. Prod., 1990, 53, 609-614.
24. 16. Structure 10 has been shown to be the unnatural enantiomer: Cordero, F. M.; Cicchi, S.; Goti, A.; Brandi, A., Tetrahedron Lett., 1994, 35, 949-952; Gurjar, M. K.; Ghosh, L.; Syamala, M.; Jayasree, V., Tetrahedron Lett., 1994, 35, 8871-8872. The natural product (the (-)-isomer) is therefore ent-10 at variance with the original report: Pastuszak, I.; Molyneux, R.; James, L. F.; Elbein, A. D., Biochemistry, 1990, 29, 1886-1891; Molyneux, R., J. Nat. Prod., 1990, 53, 609-614.
25. 16. Structure 10 has been shown to be the unnatural enantiomer: Cordero, F. M.; Cicchi, S.; Goti, A.; Brandi, A., Tetrahedron Lett., 1994, 35, 949-952; Gurjar, M. K.; Ghosh, L.; Syamala, M.; Jayasree, V., Tetrahedron Lett., 1994, 35, 8871-8872. The natural product (the (-)-isomer) is therefore ent-10 at variance with the original report: Pastuszak, I.; Molyneux, R.; James, L. F.; Elbein, A. D., Biochemistry, 1990, 29, 1886-1891; Molyneux, R., J. Nat. Prod., 1990, 53, 609-614.
26. 17. Wong, C. M.; Buccini, J.; Raa, J. T., Can. J. Chem., 1968, 46, 3091-3094; Arakawa, Y.; Yoshifuji, S., Chem. Pharm. Bull., 1991, 39, 2219-2224.
27. 17. Wong, C. M.; Buccini, J.; Raa, J. T., Can. J. Chem., 1968, 46, 3091-3094; Arakawa, Y.; Yoshifuji, S., Chem. Pharm. Bull., 1991, 39, 2219-2224.
28. 3 (1.20 ppm) 10.7% 2.1% - 14% - -
29. 19. Pilcher, A. S.; DeShong, P., J. Org. Chem., 1993, 58, 5130-5134.
30. 20. All new compounds exhibited the expected spectroscopic and analytical or accurate mass data.