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Conformational Restriction of the Calix[6]arene Macrocycle by the Ritter Reaction

  1. Ivan M. Vatsouro1,
  2. Elvira A. Shokova1,
  3. Alla K. Shestakova2,
  4. Vyacheslav A. Chertkov1,
  5. Vladimir V. Kovalev1

Article first published online: 10 NOV 2005

DOI: 10.1002/ejoc.200500604

Issue

European Journal of Organic Chemistry

European Journal of Organic Chemistry

Volume 2006, Issue 2, pages 522–530, January 2006

Additional Information

How to Cite

Vatsouro, I. M., Shokova, E. A., Shestakova, A. K., Chertkov, V. A. and Kovalev, V. V. (2006), Conformational Restriction of the Calix[6]arene Macrocycle by the Ritter Reaction. Eur. J. Org. Chem., 2006: 522–530. doi: 10.1002/ejoc.200500604

Author Information

  1. 1

    Department of Chemistry, M. V. Lomonosov Moscow State University, Lenin’s Hills, 119992 Moscow, Russia

  2. 2

    State Research Institute of the Chemistry and Technology of Organoelement Compounds, Sh. Entuziastov, 38, 111123 Moscow, Russia

Publication History

  1. Issue published online: 2 JAN 2006
  2. Article first published online: 10 NOV 2005
  3. Manuscript Received: 9 AUG 2005

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Keywords:

  • Calixarenes;
  • Amides;
  • Regioselectivity;
  • Conformation analysis;
  • Adamantane

Abstract

Herein we report on the development of a novel and efficient approach to the restriction of the conformational mobility of calix[6]arenes. The method involves the addition of tertiary alcohols to calix[6]arenes with one, three and six cyanomethoxy groups attached to the lower rim under modified Ritter reaction conditions. Alkylation of monocyanomethoxy-p-tert-butylcalix[6]arene (1) and 37,39,41-trimethoxy-38,40,42-tricyanomethoxy-p-tert-butylcalix[6]arene (2) with 3-R-1-adamantanols (R = H, CH2COOH) in trifluoroacetic acid afforded the corresponding mono- and triamides with cone-like conformations. The partial alkylation of hexanitrile derivatives showed unexpected regioselectivity. Addition of 1-adamantanol or tert-butyl alcohol to hexacyanomethoxy-p-X-calix[6]arenes 3a–c (X = tert-butyl, 1-adamantyl, 3-methoxycarbonylmethyl-1-adamantyl) gave 37,40-dinitrile-38,39,41,42-tetraamides as the major products. These tetraamides are conformationally restricted in solution over a wide range of temperatures and adopt a flattened 1,2,3-alternate conformation, as shown by 2D and variable-temperature NMR experiments. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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