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Synlett 2005(6): 0879-0891  
DOI: 10.1055/s-2005-864832
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

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

Paris E. Georghiou*a, Zhaopeng Lib, Muhammad Ashramc, Sultan Chowdhuryd, Shehadeh Mizyede, Anh Huu Trana, Hassan Al-Saraierha, David O. Millera
a Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland and Labrador, A1B 3X7, Canada
e-Mail: parisg@mun.ca;
b Crompton Co., 565 Coronation Drive West Hill, Ontario, M1E 2K3, Canada
c Department of Chemistry, Mu"Tah University, Karak, Jordan
d Xenon Pharmaceuticals Inc., 3650 Gilmore Way, Burnaby, BC, V5G 4W8, Canada
e Department of Chemistry, Yarmouk University, Irbid, Jordan
Further Information

Publication History

Received 18 August 2004
Publication Date:
23 March 2005 (online)

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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

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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.