Synthesis 2015; 47(11): 1678-1682
DOI: 10.1055/s-0034-1380413
paper
© Georg Thieme Verlag Stuttgart · New York

A Tetrahydroxycalix[4]arene Derivative with All Bridges Monosubstituted with Methoxy Groups

Norbert Itzhak
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem­ 91904, Israel   Email: silvio.biali@mail.huji.ac.il
,
Silvio E. Biali*
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem­ 91904, Israel   Email: silvio.biali@mail.huji.ac.il
› Author Affiliations
Further Information

Publication History

Received: 15 December 2014

Accepted after revision: 12 February 2015

Publication Date:
18 March 2015 (online)


Abstract

Reduction of the carbonyl groups of tetrahydroxyketocalix[4]arene with NaBH4 in propan-2-ol, followed by heating the product to reflux in MeOH–H2SO4, yields a mixture of stereoisomers of the tetrahydroxycalix[4]arene derivative with all bridges monosubstituted by a methoxy group. To structurally characterize the compound, the mixture of isomers was derivatized by reaction with di-tert-butyl dicarbonate–DMAP. X-ray crystal structure analysis of the all-cis isomer of the product (obtained by fractional crystallization), corroborates the presence of Boc protecting groups at the lower rim (and thus underivatized OH groups in the starting material), and four methoxy groups at the bridges.

Supporting Information

 
  • References


    • For reviews on calixarenes, see:
    • 1a Calixarenes, A Versatile Class of Macrocyclic Compounds. Vicens J, Böhmer V. Kluwer; Dordrecht: 1991
    • 1b Shinkai S. Tetrahedron 1993; 49: 8933
    • 1c Böhmer V. Angew. Chem., Int. Ed. Engl. 1995; 34: 713
    • 1d Gutsche CD. Aldrichimica Acta 1995; 28: 3
    • 1e Pochini A, Ungaro R In Comprehensive Supramolecular Chemistry . Vol. 2. Vögtle F. Pergamon Press; Oxford: 1996: 103
    • 1f Gutsche CD. Calixarenes Revisited. Royal Society of Chemistry; Cambridge: 1998
    • 1g Calixarenes 2001 . Asfari Z, Böhmer V, Harrowfield J, Vicens J. Kluwer Academic Publishers; Dordrecht: 2001
    • 1h Böhmer V. The Chemistry of Phenols . Rappoport Z. Wiley; Chichester: 2003. Chap. 19
    • 1i Gutsche CD. Calixarenes. An Introduction . 2nd ed. Royal Society of Chemistry; Cambridge: 2008
    • 2a Görmar G, Seiffarth K, Schultz M, Zimmermann J, Flämig G. Makromol. Chem. 1990; 191: 81
    • 2b See also: Ninagawa A, Cho K, Matsuda H. Makromol. Chem. 1985; 186: 1379

      See also:
    • 3a Seri N, Simaan S, Botoshansky M, Kaftory M, Biali SE. J. Org. Chem. 2003; 68: 7140
    • 3b Seri N, Thondorf I, Biali SE. J. Org. Chem. 2004; 69: 4774
  • 4 For a recent photochemical synthesis of the ketocalix[4]arene 1b, see: Fischer C, Lin G, Seichter W, Weber E. Tetrahedron Lett. 2013; 54: 2187
    • 5a Kogan K, Biali SE. Org. Lett. 2007; 9: 2393
    • 5b Poms D, Itzhak N, Kuno L, Biali SE. J. Org. Chem. 2014; 79: 538
    • 6a Kuno L, Seri N, Biali SE. Org. Lett. 2007; 9: 1577
    • 6b Kuno L, Biali SE. J. Org. Chem. 2009; 74: 48
    • 6c Kuno L, Biali SE. Org. Lett. 2009; 11: 3662

      For selected synthetic methods for the preparation of calixarenes substituted at the methylene bridges, see for example:
    • 7a Sartori G, Maggi R, Bigi F, Arduini A, Pastorio A, Porta C. J. Chem. Soc., Perkin Trans. 1 1994; 1657
    • 7b Biali SE, Böhmer V, Cohen S, Ferguson G, Grüttner C, Grynszpan F, Paulus EF, Thondorf I, Vogt W. J. Am. Chem. Soc. 1996; 118: 12938
    • 7c Klenke B, Näther C, Friedrichsen W. Tetrahedron Lett. 1998; 39: 8967
    • 7d Middel O, Greff Z, Taylor NJ, Verboom W, Reinhoudt DN, Snieckus V. J. Org. Chem. 2000; 65: 667
    • 7e Scully PA, Hamilton TM, Bennett JL. Org. Lett. 2001; 3: 2741
    • 7f Agbaria K, Biali SE. J. Am. Chem. Soc. 2001; 123: 12495
    • 7g Kumar SK, Chawla HM, Varadarajan R. Tetrahedron Lett. 2002; 43: 7073
    • 7h Kogan K, Columbus I, Biali SE. J. Org. Chem. 2008; 73: 7327
    • 7i Gopalsamuthiram V, Predeus AV, Huang RH, Wulff WD. J. Am. Chem. Soc. 2009; 131: 18018
    • 7j For a review on calixarenes modified at the methylene bridges, see: Sliwa W, Deska M. ARKIVOC 2012; (i): 173
  • 8 Columbus I, Biali SE. J. Org. Chem. 2008; 73: 2598

    • See, for example: 
    • 9a Alfieri C, Dradi E, Pochini A, Ungaro R. Gazz. Chim. Ital. 1989; 119: 335
    • 9b Biali SE, Böhmer V, Brenn J, Frings M, Thondorf I, Vogt W, Wöhnert J. J. Org. Chem. 1997; 62: 8350
  • 10 Itzhak N, Biali SE. J. Org. Chem. 2010; 75: 3437
  • 11 CCDC-1053221 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; E-mail: deposit@ccdc.cam.ac.uk.