Calixnaphthalenes: Deep, Electron-Rich Naphthalene Ring-Containing Calixarenes. The First Decade.

Abstract

The first naphthalene ring-based analogues of the better-known and extensively studied calixarenes were synthesized in 1993. Since that time, our group has focused its research on the design and synthesis of other ‘calixnaphthalenes’. These endeavours are motivated partly due to the synthetic challenges which they provide, and to the challenges in deciphering their structural and complexation properties. Calixnaphthalenes offer several advantages over their calixarene analogues. Among these are the facts that they can form deeper, more electron-rich and in some cases, chiral, cavities. They also provide a wide range of potential new scaffolds upon which to design and build new receptors for neutral, or charged guest species. Their supramolecular complexation properties have barely been explored as yet since in most cases, only relatively small quantities only of these compounds have been obtained. In this review, all of the known, and previously unreported calixnaphthalenes are described. As well, some of the compounds, which are described, are still subjects of ongoing research.

• 1 Introduction

• 2 Exo-calix[4]naphthalenes Derived from 1-Naphthol

• 3 Exo-calix[4]naphthalenes Derived from 1,8-Naphthalenesultone

• 4 Endo-calix[4]naphthalenes Derived from 2-Naphthol

• 4.1 C₄-Symmetrical Endo-calix[4]naphthalenes

• 4.2 Ethoxycarbonylmethoxy Esters Derived from 7 and 16

• 4.3 Alkyl Ethers Derived from 7 and 16

• 4.4 Spiro- and Bis(spirodienone) Derivatives of 7 and 16

• 4.5 C₂-Symmetrical Endo-calix[4]naphthalenes

• 4.6 C₂-Symmetrical ‘Endo-exo’-calix[4]naphthalenes

• 5 Endo-isocalix[4]naphthalenes Derived from
  2,3-Dihydroxynaphthalene

• 6 ‘Expanded’ Calix[4]naphthalenes

• 7 Other Naphthalene-Containing Calixarenes

• 8 Dihomocalix[4]naphthalenes

• 9 Hexahomotrioxacalix[3]naphthalenes

• 10 Lower-Rim Functionalized Hexahomotrioxacalix[3]naphthalenes

• 11 Tetrahomodioxacalix[4]naphthalenes

• 12 Hexahomodioxacalix[4]naphthalenes

• 13 Octahomotetraoxaisocalix[4]naphthalenes

• 14 Conclusions

Key words

calixnaphthalenes - calixarenes - naphthalene - formaldehyde - 1-naphthol - 1-naphthol - 2,3-dihydroxynaphthalene - supra­molecular complexes - host-guest complexes - fullerenes

References

• 1 Georghiou PE. Ho CK. Can. J. Chem.  1989,  67:  871 ; and references cited therein
• 2 Georghiou PE. Li Z. Tetrahedron Lett.  1993,  34:  2887 
• 3 Georghiou PE. Li Z. J. Incl. Phenom.  1994,  19:  55 
• 4 Zincke A. Ziegler E. Ber.  1944,  77:  264 
• 5 Walker JF. Formaldehyde   A.C.S. Monograph Series, No. 159, Reinhold Publishing Corp.; New York: 1964. and references cited therein
• 6 Breslauer J. Pictet A. Ber.  1907,  40:  3785 
• For recent monographs see:
• 7a Gutsche CD. Calixarenes Revisited, In Supramolecular Chemistry   Stoddard JF. Royal Society of Chemistry; Cambridge: 1998. 
• 7b Calixarenes in Action   Mandolini L. Ungaro R. Imperial College Press; London, England: 2000. 
• 7c Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic Publishers; Dordrecht: 2001. 
• 9 Andreetti GD. Böhmer V. Jordon JG. Tabatabai M. Ugozzoli F. Vogt W. Wolff W. J. Org. Chem.  1993,  58:  4023 
• 10a Poh B.-L. Lim CS. Khoo KS. Tetrahedron Lett.  1989,  30:  1005 
• 10b

  For a different interpretation of the structures of products obtained from the reaction of formaldehyde with chromotropic acid (4,5-dihydroxy-2,7-naphthalenedisulfonic acid) under similar conditions, see ref. 1.

• 11 Georghiou PE. Ashram M. Li Z. Chaulk SG. J. Org. Chem.  1995,  60:  7284 
• 12 Georghiou PE. Li Z. Ashram M. J. Org. Chem.  1998,  63:  3748 
• 15a For a recent discussion on ‘inherent chirality’ see: Dalla Cort A. Mandolini L. Pasquini C. Schiaffino L. New J. Chem.  2004,  28:  1198 
• 15b For a discussion of inherently chiral calixarenes see: Böhmer V. Kraft D. Tabatabai M. J. Incl. Phenom.  1994,  19:  3 
• 17 Chowdhury S. Ph.D. Dissertation   Memorial University of Newfoundland; Newfoundland and Labrador, Canada: 2001. 
• 18 Giddings S. M.Sc. Thesis   Memorial University of Newfoundland; Newfoundland and Labrador, Canada: 2003. 
• 19 Shorthill BJ. Avetta CT. Glass TE. J. Am. Chem. Soc.  2004,  126:  12732 
• 20 Mizyed S. Ph.D. Dissertation   Memorial University of Newfoundland; Newfoundland and Labrador, Canada: 2002. 
• 21 Georghiou PE. Mizyed S. Chowdhury S. Tetrahedron Lett.  1999,  40:  611 
• 22 Mizyed S. Georghiou PE. Ashram M. J. Chem. Soc., Perkin Trans. 2  2000,  277 
• 23 Mizyed S. Tremaine PR. Georghiou PE. J. Chem. Soc., Perkin Trans. 2  2001,  3 
• 25 Ashram M. Ph.D. Dissertation   Memorial University of Newfoundland; Newfoundland and Labrador, Canada: 1999. 
• 26 Iwamoto K. Shinkai S. J. Org. Chem.  1992,  57:  7066 
• 27 Aleksiuk O. Biali SE. J. Org. Chem.  1992,  57:  1943 
• 28 Georghiou PE. Ashram M. Clase HJ. Bridson JN. J. Org. Chem.  1998,  63:  1819 
• 29 Chowdhury S. Georghiou PE. J. Org. Chem.  2002,  67:  6808 
• 30 Chowdhury S. Georghiou PE. Tetrahedron Lett.  2000,  40:  7599 
• 32 Li Z. Ph.D. Dissertation   Memorial University of Newfoundland; Newfoundland and Labrador, Canada: 1996. 
• 33a Shorthill BJ. Granucci RG. Powell DR. Glass TE. J. Org. Chem.  2002,  67:  904 
• 33b Shorthill BJ. Glass TE. Org. Lett.  2001,  3:  577 
• 34 Ikeda A. Yoshimura M. Lhotak P. Shinkai S. J. Chem. Soc., Perkin Trans. 1  1996,  1945 
• 35 Georghiou PE. Li Z. Ashram M. Miller DO. J. Org. Chem.  1996,  61:  3865 
• 37a Ashram M. Mizyed S. Georghiou PE. J. Org. Chem.  2001,  66:  1473 
• 37b For the results obtained from other synthetic endeavours towards the synthesis of these compounds, see: Ashram M. Miller DO. Georghiou PE. J. Chem. Soc., Perkin Trans. 1  2002,  1470 
• 38 Tsubaki K. Mukoyoshi K. Otsubo T. Fuji K. Chem. Pharm. Bull.  2000,  48:  882 
• 39 Mizyed S. Ashram M. Miller DO. Georghiou PE. J. Chem. Soc., Perkin Trans. 2  2001,  1916 
• 40 Ashram M. Mizyed S. Georghiou PE. Org. Biomol. Chem.  2003,  1:  599 
• 42 Tran AH. Miller DO. Georghiou PE. J. Org. Chem.  2005,  70:  1115 
• 44 Named in honour of the dance-loving ‘Zorba’ character created by the acclaimed modern Greek writer Nikos Kazantzakis (1883-1957) in the popular novel ‘Zorba the Greek’ originally published in 1952. For an engaging account of the origins of various names coined by organic chemists see: Nickon A. Silversmith EF. Organic Chemistry. The Name Game   Pergamon Books, Inc.; U.K.: 1987. 
• 45a Masci B. Tetrahedron  1995,  51:  5459 
• 45b Masci B. Finelli M. Varrone M. Chem.-Eur. J.  1998,  4:  2018 
• 45c Masci B. In Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic Publishers; Dordrecht, The Netherlands: 2001. 
• 45d Masci B. J. Org. Chem.  2001,  66:  1497 
• 45e Masci B. Tetrahedron  2001,  57:  2841 
• 46 Sarri P., Venturi V., Cuda F., Roelens S.; J. Org. Chem.; 2004, 69: 3654

8

The Chemical Abstracts names for compounds 1-3, respectively, are 6H,14H,22H,30H-5,31:7,13:15,21:23,29-tetramethenotetrabenzo[a,g,m,s]cyclotetra-cosene-8,16,24,32-tetrol, 7H,15H,23H,31H-6,32:8,14:16,22:24,30-tetramethenotetra-benzo[a,f,l,s]cyclotetracosene-5,13,17,25-tetrol, and 6H,14H,22H,30H-5,31:7,13:15,21:23,29-tetramethenotetrabenzo[a,f,l,r]cyclo-tetracosene-12,20,28,32-tetrol.

13

Unpublished results of a limited in vivo study, and in vitro assays conducted by the National Institutes of Health, Bethesda, Maryland, USA (1997-1999).

14

This arbitrary numbering system used to identify the positions on the A-ring of the naphthyl unit where the methylene bridges are located is based upon the usual numbering system used to designate the carbon atoms on a naphthalene ring.

16

Molecular modeling was conducted using SpartanPro V1.1 Molecular Modeling Software from Wavefunction, Irving, CA., USA.

24

See ref.19 and references cited therein for a review of some of these considerations.

31

The name ‘isocalixnaphthalenes’ for such 1,4- or para-linked compounds was suggested to us by Professor C. David Gutsche, the originator of the name ‘calixarenes’; personal communication, October 21, 2004.

36

Ashram, M.; Tran, A. H.; Georghiou, P. E.; manuscript in preparation.

41

Al-Saraierh, H.; Georghiou, P. E.; unpublished results.

43

As a ‘cyclophane’ this compound can be designated as a tetraoxa[3.3.3.3]para(2,3-dihydroxy)naphthaleneophane.

47

R. Aldington, British Poet, Novelist, Literary Scholar, July 8, 1892-July 27, 1962. The quotation is from Life for Life"s Sake, Chapter 5, 1941. Mike Kesterton of the ‘Globe and Mail’ is acknowledged for providing the reference.