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For a review on the oxidation and reduction of calixarene aromatic rings, see: (a) Biali, S. E. In Calixarenes 2001; Asfari, Z., Böhmer, V., Harrowrïeld, J., Vicens J., Eds.; Kluwer: Dordrecht, 2001; Chapter 14, pp 266-279.
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0032545006
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For examples of calixcyclohexanol derivatives, see ref 7a and: (a) Columbus, I, Haj-Zaroubi, M, Biali, S. E. J. Am. Chem. Soc. 1998, 120, 11806 and references therein
-
For examples of calixcyclohexanol derivatives, see ref 7a and: (a) Columbus, I.; Haj-Zaroubi, M.; Biali, S. E. J. Am. Chem. Soc. 1998, 120, 11806 and references therein.
-
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30
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85045589692
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31
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33947118480
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Polar, nonionic, calixarene derivatives have also been obtained by appending hydrophilic groups: (a) Grote Gansey, M. H. B.; Steemers, F. J.; Verboom, W.; Reinhoudt, D. N. Synthesis 1997, 643.
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Polar, nonionic, calixarene derivatives have also been obtained by appending hydrophilic groups: (a) Grote Gansey, M. H. B.; Steemers, F. J.; Verboom, W.; Reinhoudt, D. N. Synthesis 1997, 643.
-
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-
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32
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0034751995
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and references therein
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(b) Segura, M.; Sansone, F.; Casnati, A.; Ungaro, R. Synthesis 2001, 2105 and references therein.
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Synthesis
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Segura, M.1
Sansone, F.2
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4544358510
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35
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0007006780
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37
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33947190288
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See the Supporting Information for additional details
-
See the Supporting Information for additional details.
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-
-
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38
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33947125846
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The X-ray analysis supports the gross structure, although the R factor was 13%.
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The X-ray analysis supports the gross structure, although the R factor was 13%.
-
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-
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39
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33947102906
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This unexpected reaction outcome is likely the result of an initial epoxy interchange to give II (Payne's rearrangement: Payne, G. B. J. Org. Chem. 1962, 27, 3819, which is possible because of the trans disposition of the epoxy and secondary hydroxyl groups, Chemical Equation Presented) Reductive opening of the new epoxy group by SN2 attack of the hydride ion would then give III, in which an intramolecular S N2 attack of the alkoxide group to the second epoxide would give rise to the oxetane ring in IV
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N2 attack of the alkoxide group to the second epoxide would give rise to the oxetane ring in IV.
-
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-
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40
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38849162458
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In fact, cyclitols are cycloalkanes containing one hydroxyl group on each of three or more ring atoms Angyal, S. J, Andersen, C, Cahn, R. S, Dowson, R. M. C, Hoffmann-Ostenhof, O, Klyne, W, Posternack, T. Pure Appl. Chem. 1974, 37, 283
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In fact, cyclitols are cycloalkanes containing one hydroxyl group on each of three or more ring atoms (Angyal, S. J.; Andersen, C.; Cahn, R. S.; Dowson, R. M. C.; Hoffmann-Ostenhof, O.; Klyne, W.; Posternack, T. Pure Appl. Chem. 1974, 37, 283).
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42
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0000970872
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Diaz, S.G.1
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0025782420
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Iwamoto, K.; Araki, K.; Shinkai, S. Tetrahedron 1991, 47, 4325.
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Tetrahedron
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-
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Iwamoto, K.1
Araki, K.2
Shinkai, S.3
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46
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33947117722
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Analogous oxygenation of 6 with t-BuOK in dry DMF for 17 h, at 80°C, followed by treatment with t-BuOOH/t-BuOK, resulted in the formation of 7 in 17% yield.
-
Analogous oxygenation of 6 with t-BuOK in dry DMF for 17 h, at 80°C, followed by treatment with t-BuOOH/t-BuOK, resulted in the formation of 7 in 17% yield.
-
-
-
-
47
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33947132471
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In accordance with a previously used notation,10 we indicate with X (or N) the ring bearing exo-epoxides or endo-epoxides
-
10 we indicate with X (or N) the ring bearing exo-epoxides (or endo-epoxides).
-
-
-
-
48
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33947097735
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MacroModel, version 9.0; Schrödinger, LLC: New York, 2005
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MacroModel, version 9.0; Schrödinger, LLC: New York, 2005.
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49
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33947107294
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In accordance with this high difference of energy, only signals related to cone conformer 9 are present in its 1H NMR spectrum. Dynamic NMR studies (400 MHz) showed that calixcyclitol 9 is fixed in this cone conformation at room temperature and indicated a coalescence of both the ArCH2 signals at temperatures higher than 393 K in TCDE. Therefore, an energy barrier higher than 17.2 kcal/mol can be estimated for its conformational inversion. Similar higher-energy barriers for the through-the-annulus rotation of cyclohexanol rings with respect to phenol rings were previously evidenced by Biali for calixcyclohexanol derivatives. 8a,b
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8a,b
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