(organic chemistry) A molecule composed of an aromatic ring (most frequently a benzene ring) and an aliphatic unit which forms a bridge between two (or more) positions of the aromatic ring.
Cyclophane
| Sci-Tech Dictionary: cyclophane |
(′sī·klə′fān)
| 5min Related Video: Cyclophane |
| Sci-Tech Encyclopedia: Cyclophane |
A molecule composed of two building blocks: an aromatic ring (most frequently a benzene ring) and an aliphatic unit forming a bridge between two (or more) positions of the aromatic ring. Those cyclophanes that contain heteroatoms in the aromatic part are generally called phanes, as “cyclo” in cyclophanes more strictly means that only benzene rings are present in addition to aliphatic bridges. Phane molecules containing hetero atoms in the aromatic ring (for example, nitrogen or sulfur) are called heterophanes, while in heteraphanes they are part of the aliphatic bridge.
Cyclophanes usually are not at all planar molecules; they exhibit an interesting stereochemistry (arrangement of atoms in three-dimensional space); molecular parts are placed and sometimes fixed in unusual orientations toward each other, and often the molecules are not rigid but (conformationally) flexible. Ring strain and, as a consequence, deformation of the benzene rings out of planarity are often encountered. Electronic interactions between aromatic rings fixed face to face can take place. In addition, influence on substitution reactions in the aromatic rings results; that is, substitutents in one ring induce transannular electronic effects in the other ring, often leading to unexpected products. See also Chemical bonding; Conformational analysis; Stereochemistry.
Cyclophanes have become important in host-guest chemistry and supramolecular chemistry as they constitute host compounds for guest particles because of their cavities. Recognition processes at the molecular level are understood to mean the ability to design host molecules to encompass or attach selectively to smaller, sterically complementary guests in solution—by analogy to biological receptors and enzymes. For this reason, water-soluble cyclophanes were synthesized; they have the ability to include nonpolar guest molecules in aqueous solution. See also Cage hydrocarbon; Molecular recognition; Polar molecule.
Cyclophanes also exist in nature as alkaloids, cytotoxic agents, antibiotics, and many cyclopeptides. With the possibility of locating groups precisely in space, cyclophane chemistry has provided building units for molecular niches, nests, hollow cavities, multifloor structures, helices, macropolycycles, macro-hollow tubes, novel ligand systems, and so on. Cyclophane chemistry has become a major component of supramolecular chemistry, molecular recognition, models for intercalation, building blocks for organic catalysts, receptor models, and variation of crown ethers and cryptands. See also Macrocyclic compound; Supramolecular chemistry.
| Wikipedia: Cyclophane |
A cyclophane is a hydrocarbon consisting of an aromatic unit (typically a benzene ring) and an aliphatic chain that forms a bridge between two non-adjacent positions of the aromatic ring. More complex derivatives with multiple aromatic units and bridges forming cagelike structures are also known. Cyclophanes are well-studied in organic chemistry because they adopt unusual chemical conformations due to build-up of strain. Despite this, cyclophane structures are not unknown to biomolecules.
![Scheme 2. [6]paracyclophanes](http://en.wikipedia.org/wiki/File:-6-cyclophanes.png)
Basic cyclophane types are [n]metacyclophanes (I) in scheme 1, [n]paracyclophanes (II) and [n,n']cyclophanes (III). the prefixes meta and para correspond to the usual arene substitution patterns and n refers to the number of atoms making up the bridge.
Contents |
Structure
Paracyclophanes adopt the boat conformation normally observed in cyclohexanes but are still able to retain aromaticity. The smaller the value of n the larger the deviation from aromatic planarity. In [6]paracyclophane which one of the stable cyclophanes X-ray crystallography shows that the aromatic bridgehead carbon atom makes an angle of 20.5° with the plane. The benzyl carbons deviate by another 20.2°. The carbon to carbon bond length alternation has increased from 0 for benzene to 39 pm.[1][2]
In organic reactions [6]cyclophane tends to react as a diene derivative and not as an arene. With bromine it gives 1,4-addition and with chlorine the 1,2-addition product forms.
Yet the proton NMR spectrum displays the aromatic protons and their usual deshielded positions around 7.2 ppm and the central methylene protons in the aliphatic bridge are even severely deshielded to a position of around - 0.5 ppm, that is, even deshielded compared to the internal reference tetramethylsilane. With respect to the diamagnetic ring current criterion for aromaticity this cyclophane is still aromatic.
One particular research field in cyclophanes involves probing just how close atoms can get above the center of an aromatic nucleus.[3] In so-called in-cyclophanes with part of the molecule forced to point inwards one of the closest hydrogen to arene distances experimentally determined is just 168 picometer.
A non-bonding nitrogen to arene distance of 244 pm is recorded for a pyridinophane and in the totally weird superphane the two benzene rings are separated by a mere 262 pm. Another representative of this group are in-methylcyclophanes.
Synthetic methods
[6]paracyclophane can be synthesized[4][5] in the laboratory by a Bamford-Stevens reaction with spiro ketone 1 in scheme 3 rearranging in a pyrolysis reaction through the carbene intermediate 4. The cyclophane can be photochemically converted to the Dewar benzene 6 and back again by application of heat. A separate route to the Dewar form is by a cationic silver perchlorate induced rearrangement reaction of the bicyclopropenyl compound 7.
![Scheme 3. [6]paracyclophane synthesis](http://en.wikipedia.org/wiki/File:-6-cyclophaneSynthesis.png)
Metaparacyclophanes constitute another class of cyclophans like the [14][14]metaparacyclophane[6] in scheme 4[7] featuring a in-situ Ramberg-Bäcklund Reaction converting the sulfone 3 to the alkene 4.
![Scheme 4. [14][14]metaparacyclophane](http://en.wikipedia.org/wiki/File:Metaparacyclophane.png)
Naturally occurring cyclophanes
Despite carrying strain, the cyclophane motif does exist in nature. One example of a metacyclophane is cavicularin.
Haouamine A is a paracyclophane found in a certain species of tunicate. Because of its potential application as an anticancer drug it is also available from total synthesis via an alkyne - pyrone Diels-Alder reaction in the crucial step with expulsion of carbon dioxide (scheme 5).[8]
In this compound the deviation from planarity is 13° for the benzene ring and 17° for the bridgehead carbons.[9] An alternative cyclophane formation strategy in scheme 6[10] was developed based on aromatization of the ring well after the formation of the bridge.
[n,n]Paracyclophanes
A well exploited member of the [n,n]paracyclophane family is [2,2]paracyclophane. One method for its preparation is by a 1,6-Hofmann elimination:[11]
The [2.2]paracyclophane-1,9-diene has been applied in ROMP to a poly(p-phenylene vinylene) with alternating cis-alkene and trans-alkene bonds using Grubbs' second generation catalyst:[12]
The driving force for ring-opening and polymerization is strain relief. The reaction is believed to be a living polymerization due to the lack of competing reactions.
Because the two benzene rings are in close proximity this cyclophane type also serves as guinea pig for photochemical dimerization reactions as illustrated by this example:[13]
The product formed has an octahedrane skeleton. Interestingly when the amine group is replaced by a methylene group no reaction takes place: the dimerization requires through-bond overlap between the aromatic pi electrons and the sigma electrons in the C-N bond in the reactants LUMO.
References
- ^ Synthesis and molecular structure of (Z)-[6]Paracycloph-3-enes Yoshito Tobe, Kenichi Ueda, Teruhisa Kaneda, Kiyomi Kakiuchi, Yoshinobu Odaira, Yasushi Kai, Nobutami Kasai J. Am. Chem. Soc.; 1987; 109(4); 1136-1144. Abstract
- ^ J. Hunger, C. Wolff, W. Tochtermann, E-M. Peters, K.Peters, H.G. von Schering Chem. Ber., 119, 2698 (1986)
- ^ Molecular Iron Maidens: Ultrashort Nonbonded Contacts in Cyclophanes and Other Crowded Molecules Robert A. Pascal, Jr Eur. J. Org. Chem. 2004, 3763-3771 doi:10.1002/ejoc.200400183
- ^ [6]Paracyclophane Vinayak V. Kane, Anthony D. Wolf, Maitland Jones, , Jr. J. Am. Chem. Soc.; 1974; 96(8); 2643-2644. Abstract
- ^ Interconversion of [6]paracyclophane and 1,4-hexamethylene(Dewar benzene) Seetha L. Kammula, Linda D. Iroff, Maitland Jones, , Jr. J. W. Van Straten, W. H. De Wolf, F. Bickelhaupt J. Am. Chem. Soc.; 1977; 99(17); 5815-5815. Abstract
- ^ [14][14]Metaparacyclophane: First Example of an [m][n]MetaparacyclophaneChunmei Wei, Kai-For Mo, and Tze-Lock Chan J. Org. Chem.; 2003; 68(7) pp 2948 - 2951; (Note) Abstract
- ^ Scheme 4. Reaction scheme: with para-ring in place ring closure of meta part by nucleophilic displacement of dibromide by disulfide. Then oxidation of sulfide to sulfone by hydrogen peroxide followed by in-situ Ramberg-Bäcklund Reaction with halide donor dibromodifluoromethane and base potassium hydroxide. Final step hydrogenation pf alkene by hydrogen and palladium on carbon
- ^ Total Synthesis of (±)-Haouamine A Phil S. Baran and Noah Z. Burns J. Am. Chem. Soc.; 2006; ASAP Web Release Date: 04-Mar-2006; Abstract The authors mark the biosynthetic origin as mysterious
- ^ Synthesis of the 3-Aza-[7]-paracyclophane Core of Haouamine A and B Peter Wipf and Markus Furegati Org. Lett.; 2006; 8(9) pp 1901 - 1904; (Letter) Abstract
- ^ Scheme 6. Reaction scheme: step I elimination reaction of methanol with trifluoroethanol and diisopropylamine, step II methylation with dimethyl sulfate. Ns = Nosylate
- ^ Organic Syntheses, Coll. Vol. 5, p.883 (1973); Vol. 42, p.83 (1962) Link.
- ^ Soluble Poly(p-phenylenevinylene)s through Ring-Opening Metathesis Polymerization Chin-Yang Yu and Michael L. Turner Angew. Chem. Int. Ed. 2006, 45, 7797 –7800 doi:10.1002/anie.200602863
- ^ Photoreaction of a 2,11-Diaza[3.3]paracyclophane Derivative: Formation of Octahedrane by Photochemical Dimerization of Benzene Hideki Okamoto, Kyosuke Satake, Hiroyuki Ishida, and Masaru Kimura J. Am. Chem. Soc.; 2006; 128(51) pp 16508 - 16509; (Communication) doi:10.1021/ja067350r
This entry is from Wikipedia, the leading user-contributed encyclopedia. It may not have been reviewed by professional editors (see full disclaimer)
Learn More
 | Molecular recognition |
| Macrocyclic compound (organic chemistry) |
| Supramolecular chemistry |
Post a question - any question - to the WikiAnswers community:
Copyrights:
 |
 | Sci-Tech Dictionary. McGraw-Hill Dictionary of Scientific and Technical Terms. Copyright © 2003, 1994, 1989, 1984, 1978, 1976, 1974 by McGraw-Hill Companies, Inc. All rights reserved. Read more |
|
| Sci-Tech Encyclopedia. McGraw-Hill Encyclopedia of Science and Technology. Copyright © 2005 by The McGraw-Hill Companies, Inc. All rights reserved. Read more |
 |
| Wikipedia. This article is licensed under the Creative Commons Attribution/Share-Alike License. It uses material from the Wikipedia article "Cyclophane". Read more |
ADVERTISEMENT
Mentioned in
