Revised structure of squalene-derived pentaTHF polyether, glabrescol, through its enantioselective total synthesis: Biogenetically intriguing C(s) vs C2 symmetric relationships [6]

Journal of the American Chemical Society

Volumn 122, Issue 29, 2000, Pages 7124-7125

  Morimoto, Yoshiki ^a   Iwai, Toshiyuki ^a   Kinoshita, Takamasa ^a  

^a Osaka Prefecture University   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

POLYETHER; SQUALENE DERIVATIVE; TRITERPENE DERIVATIVE;

CHEMICAL STRUCTURE; CYCLIZATION; LETTER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034718085     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0007657     Document Type: Letter

References (29)

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15. s-symmetric diastereomers: (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
16. s-symmetric diastereomers: (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
17. s-symmetric diastereomers: (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
18. s-symmetric diastereomers: (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
19. s-symmetric diastereomers: (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
20. s-symmetric diastereomers: (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
21. Although there is no report on the biological activities of glabrescol, the vicinal pentaTHF linkage may be expected to exhibit ionophoric functions as well as cytotoxicities. See: (a) Schultz, W. J.; Etter, M. C.; Pocius, A. V.; Smith, S. J. Am. Chem. Soc. 1980, 102, 7981-7982. (b) Wagner, H.; Harms, K.; Koert, U.; Meder, S.; Boheim, G. Angew. Chem., Int. Ed. Engl. 1996, 35, 2643-2646.
22. Although there is no report on the biological activities of glabrescol, the vicinal pentaTHF linkage may be expected to exhibit ionophoric functions as well as cytotoxicities. See: (a) Schultz, W. J.; Etter, M. C.; Pocius, A. V.; Smith, S. J. Am. Chem. Soc. 1980, 102, 7981-7982. (b) Wagner, H.; Harms, K.; Koert, U.; Meder, S.; Boheim, G. Angew. Chem., Int. Ed. Engl. 1996, 35, 2643-2646.
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24. Although it was envisaged that the desirable pentaTHF 1 could be synthesized from the diol 10 in a single step by the two-directional and sequential oxidative cyclizations, direct oxidative cyclizations of the diol 10 unfortunately resulted in complex mixtures.
25. The relative stereochemistry between the 2- and 5-positions within each THF ring, except for the central THF ring, in the pentaTHF ethers 1. 13-15, 4, and natural glabrescol generously supplied by Jacobs was determined by the presence of NOEs observed between the oxymethine proton and the methyl group in a relationship cis to that proton in their NOE spectra. See the Supporting Information.
26. 3, MeOH.
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29. D between Jacobs et al. (ref 8) and us is not clear at present.