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Resorcinarene

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In chemistry, a resorcinarene (also resorcarene or calix[4]resorcinarene) is a macrocycle, or a cyclic oligomer, based on the condensation of resorcinol (1,3-dihydroxybenzene) and an aldehyde. Resorcinarenes are a type of calixarene. Other types of resorcinarenes include the related pyrogallolarenes and octahydroxypyridines, derived from pyrogallol and 2,6-dihydroxypyridine, respectively.

Resorcinarenes interact with other molecules forming a host–guest complex.[1] Resorcinarenes and pyrogallolarenes self-assemble into larger supramolecular structures. Both in the crystalline state and in organic solvents, six resorcinarene molecules are known to form hexamers with an internal volume of around one cubic nanometer (nanocapsules) and shapes similar to the Archimedean solids.[2] Hydrogen bonds appear to hold the assembly together. A number of solvent or other molecules reside inside.[3] The resorcinarene is also the basic structural unit for other molecular recognition scaffolds, typically formed by bridging the phenolic oxygens with alkyl or aromatic spacers.[4] A number of molecular structures are based on this macrocycle, namely cavitands and carcerands.

Synthesis

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The resorcinarenes are typically prepared by condensation of resorcinol and an aldehyde in acid solution. This reaction was first described by Adolf von Baeyer who described the condensation of resorcinol and benzaldehyde but was unable to elucidate the nature of the product(s). The methods have since been refined.[5][6] Recrystallization typically gives the desired isomer in quite pure form. However, for certain aldehydes, the reaction conditions lead to significant by-products. Alternative condensation conditions have been developed, including the use of Lewis acid catalysts.

Preparation of resorcin[4]arenes from resorcinol and an aldehyde
Preparation of resorcin[4]arenes from resorcinol and an aldehyde

A green chemistry procedure uses solvent-free conditions: resorcinol, an aldehyde, and p-toluenesulfonic acid are ground together in a mortar and pestle at low temperature.[7]

Structure

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Resorcinarenes can be characterized by a wide upper rim and a narrow lower rim. The upper rim includes eight hydroxyl groups that can participate in hydrogen bonding interactions. Depending on the aldehyde starting material, the lower rim includes four appending groups, usually chosen to give optimal solubility. The resorcin[n]arene nomenclature is analogous to that of calix[n]arenes, in which 'n' represents the number of repeating units in the ring. Pyrogallolarenes are related macrocycles derived from the condensation of pyrogallol (1,2,3-trihydroxybenzene) with an aldehyde.

Resorcinarenes and pyrogallolarenes self-assemble to give supramolecular assemblies. Both in the crystalline state and in solution, they are known to form hexamers that are akin to certain Archimedean solids with an internal volume of around one cubic nanometer (nanocapsules). (Isobutylpyrogallol[4]arene)6 is held together by 48 intermolecular hydrogen bonds. The remaining 24 hydrogen bonds are intramolecular. The cavity is filled by solvent.[8]

Catalysis

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The resorcinarene hexamer has been described as a yoctolitre reaction vessel.[9][10] Within the confines of the container, terpene cyclizations and iminium catalyzed reactions have been observed.[11][12]

References

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  1. ^ Aoyama Y, Tanaka Y, Toi H, Ogoshi H (1988). "Polar host–guest interaction. Binding of nonionic polar compounds with a resorcinol-aldehyde cyclooligomer as a lipophilic polar host". Journal of the American Chemical Society. 110 (2): 634–635. doi:10.1021/ja00210a073.
  2. ^ Atwood JL, Barbour LJ, Jerga A (2002). "Organization of the interior of molecular capsules by hydrogen bonding". Proceedings of the National Academy of Sciences. 99 (8): 4837–4841. Bibcode:2002PNAS...99.4837A. doi:10.1073/pnas.082659799. PMC 122679. PMID 11943875.
  3. ^ Shivanyuk A, Rebek J (2001). "Reversible encapsulation by self-assembling resorcinarene subunits". Proceedings of the National Academy of Sciences. 98 (14): 7662–7665. Bibcode:2001PNAS...98.7662S. doi:10.1073/pnas.141226898. PMC 35398. PMID 11427733.
  4. ^ Jordan, J. H.; Gibb, B. C. (2017). "1.16 - Water-Soluble Cavitands☆". In Atwood, Jerry (ed.). Comprehensive Supramolecular Chemistry II. Elsevier. pp. 387–404. ISBN 9780128031995.
  5. ^ Högberg AGS (1980). "Two stereoisomeric macrocyclic resorcinol-acetaldehyde condensation products". Journal of Organic Chemistry. 45 (22): 4498–4500. doi:10.1021/jo01310a046.
  6. ^ Högberg AGS (1980). "Cyclooligomeric phenol-aldehyde condensation products. 2. Stereoselective synthesis and DNMR study of two 1,8,15,22-tetraphenyl[14]metacyclophan-3,5,10,12,17,19,24,26-octols". Journal of the American Chemical Society. 102 (19): 6046–6050. doi:10.1021/ja00539a012.
  7. ^ Antesberger J, Cave GW, Ferrarelli MC, Heaven MW, Raston CL, Atwood JL (2005). "Solvent-free, direct synthesis of supramolecular nano-capsules". Chemical Communications. 2005 (7): 892–894. doi:10.1039/b412251h. PMID 15700072.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  8. ^ Atwood JL, Barbour LJ, Jerga A (2002). "Organization of the interior of molecular capsules by hydrogen bonding". Proceedings of the National Academy of Sciences. 99 (8): 4837–41. Bibcode:2002PNAS...99.4837A. doi:10.1073/pnas.082659799. PMC 122679. PMID 11943875.
  9. ^ Zhang, Qi; Tiefenbacher, Konrad (16 October 2013). "Hexameric Resorcinarene Capsule is a Brønsted Acid: Investigation and Application to Synthesis and Catalysis". Journal of the American Chemical Society. 135 (43): 16213–16219. doi:10.1021/ja4080375. PMID 24131349.
  10. ^ Zhang, Qi; Catti, Lorenzo; Kaila, Ville R. I.; Tiefenbacher, Konrad (2017). "To catalyze or not to catalyze: elucidation of the subtle differences between the hexameric capsules of pyrogallolarene and resorcinarene". Chemical Science. 8 (2): 1653–1657. doi:10.1039/c6sc04565k. PMC 5364520. PMID 28451294.
  11. ^ Zhang, Q.; Tiefenbacher, K. (16 February 2015). "Terpene cyclization catalysed inside a self-assembled cavity". Nature Chemistry. 7 (3): 197–202. Bibcode:2015NatCh...7..197Z. doi:10.1038/nchem.2181. PMID 25698327. S2CID 853220.
  12. ^ Bräuer, Thomas M.; Zhang, Qi; Tiefenbacher, Konrad (27 June 2016). "Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess". Angewandte Chemie International Edition. 55 (27): 7698–7701. doi:10.1002/anie.201602382. PMID 27259076. S2CID 41517528.
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