Scholl reaction
The Scholl reaction is a coupling reaction between two arene compounds with the aid of a Lewis acid and a protic acid.[1][2]
The protic acid is often an impurity in the Lewis Acid and also formed in the course of a Scholl reaction. Reagents are iron(III) chloride in dichloromethane, copper(II) chloride, PIFA and boron trifluoride etherate in dichloromethane, Molybdenum(V) chloride and lead tetraacetate with BF3 in acetonitrile [3].
Given the high reaction temperature and the requirement for strongly acidic catalysts the chemical yield often are low and the method is not a popular one. Intramolecular reactions fair better than the intermolecular ones, for instance in the organic synthesis of 9-phenylfluorene:
Or the formation of the pyrene dibenzo-(a.1)-pyrene from the anthracene] 1-phenylbenz(a)anthracene (66% yield).[4]
One study showed that the reaction lends itself to cascade reactions to form more complex polycyclic aromatic hydrocarbons [5]
In certain applications such as triphenylene synthesis this reaction is advocated as an alternative for the Suzuki reaction. A reoccurring problem is oligomerization of the product which can be prevented by blocking tert-butyl substituents [3]:
The exact reaction mechanism is not known but could very well proceed through an arenium ion. Just as in electrophilic aromatic substitution, Activating groups such as methoxy improve yield and selectivity [3]:
References
- ↑ R. Scholl, C. Seer, Ann. 394, 111 (1912).
- ↑ M B Smith, J March. March's Advanced Organic Chemistry (Wiley, 2001) (ISBN 0-471-58589-0)
- ↑ 3.0 3.1 3.2 Controlling the Scholl Reaction Benjamin T. King, Jií Kroulík, Charles R. Robertson, Pawel Rempala, Cameron L. Hilton, Justin D. Korinek, and Lisa M. Gortari J. Org. Chem.; 2007; 72(7) pp 2279 - 2288; (Article) doi:10.1021/jo061515x
- ↑ Vingiello, F. A.; Yanez, J.; Campbell, J. A. J. Org. Chem. 1971, 36, 2053-2056. (doi:10.1021/jo00814a005)
- ↑ Nanosized Molecular Propellers by Cyclodehydrogenation of Polyphenylene Dendrimers Christopher D. Simpson, Gunter Mattersteig, Kai Martin, Lileta Gherghel, Roland E. Bauer, Hans Joachim Räder, and Klaus Müllen J. Am. Chem. Soc.; 2004; 126(10) pp 3139 - 3147; (Article) doi:10.1021/ja036732j