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2. Absolute stereochemistry of ciguatoxin was determined to be one represented by structure 1, see: Satake, M.; Morohashi, A.; Yasumoto, T.; Legrand, A.-M. 38th Symposium on the Chemistry of Natural Products, Japan, Sendai, 1996, Symposium Papers, pp. 481-486.
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(d) Nicolaou, K. C. McGarry, D. G.; Somers, P. K.; Kim, B. H.; Ogilvie, W. W.; Yiannikouros, G.; Prasad, C. V. C.; Veal, C. A.; Hark, R. R. J. Am. Chem. Soc. 1990, 112, 6263-6267.
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(c) Sasaki, M.; Inoue, M.; Murata, M.; Tachibana, K. Proceedings of the International Symposium on Ciguatera and Marine Natural Products; Hokama, Y.; Scheuer, P. J.; Yasumoto, T. Eds.; Asian-Pacific Research Foundation, 1995; pp. 229-237.
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25
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0011331335
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note
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9. The trans-anti-trans arrangement of 7 was firmly established by converting it to p-bromobenzoate i and an X-ray crystallographic analysis. (equation presented)
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26
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0027983749
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and references cited therein
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10. Kadota, I.; Miura, K.; Yamamoto, Y. J. Chem. Soc., Chem. Commun. 1994, 1953-1954 and references cited therein.
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85033540923
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11. Kadota, I.; Gevorgyan, V.; Yamada, J.; Yamamoto, Y. Synlett 1991, 823-824.
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Yamamoto, Y.4
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28
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2142858450
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presence of some impurities in 9 made its optical rotational value unreliable
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12. Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092-4096; presence of some impurities in 9 made its optical rotational value unreliable.
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Ohtani, I.1
Kusumi, T.2
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Kakisawa, H.4
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29
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0011290437
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Syn-relationship between angular protons in 3 was confirmed by NOE experiments, by which the stereochemistry of the newly generated secondary hydroxyl at C8 was also assigned on the basis prominent NOEs due to H-5/H-8 and H-8/H-10
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13. Syn-relationship between angular protons in 3 was confirmed by NOE experiments, by which the stereochemistry of the newly generated secondary hydroxyl at C8 was also assigned on the basis prominent NOEs due to H-5/H-8 and H-8/H-10.
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30
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0011374604
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6α,6β = 14.0 Hz, J6α,7 = 9.8 Hz, 6α-H), 2.19 (dd, J6β,6α = 14.0 Hz, J6β,7 = 3.7 Hz, 6β-H)
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6α,6β = 14.0 Hz, J6α,7 = 9.8 Hz, 6α-H), 2.19 (dd, J6β,6α = 14.0 Hz, J6β,7 = 3.7 Hz, 6β-H).
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