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Proton-Catalyzed, Silane-Fueled Friedel-Crafts Coupling of Fluoroarenes

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Science  29 Apr 2011:
Vol. 332, Issue 6029, pp. 574-577
DOI: 10.1126/science.1202432

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Putting the F in Friedel-Crafts

The Friedel-Crafts class of reactions, among the oldest and most broadly applied in organic chemistry, form carbon-carbon bonds between aromatic rings and a variety of non-aromatic substituents, such as alkyl groups. Generally, a metal complex is used to activate chlorinated or brominated precursors of these substituents, but by using silicon-based reagents to activate a fluorinated precursor, Allemann et al. (p. 574) extend the reaction to coupling of two different aromatic sites, leading to efficient formation of elaborate polycyclic structures. The method relies on the unusual strength of silicon-fluorine bonds as a driving force.

Abstract

The venerable Friedel-Crafts reaction appends alkyl or acyl groups to aromatic rings through alkyl or acyl cation equivalents typically generated by Lewis acids. We show that phenyl cation equivalents, generated from otherwise unreactive aryl fluorides, allow extension of the Friedel-Crafts reaction to intramolecular aryl couplings. The enabling feature of this reaction is the exchange of carbon-fluorine for silicon-fluorine bond enthalpies; the reaction is activated by an intermediate silyl cation. Catalytic quantities of protons or silyl cations paired with weakly coordinating carborane counterions initiate the reactions, after which proton transfer in the final aromatization step regenerates the active silyl cation species by protodesilylation of a quaternary silane. The methodology allows the high-yield formation of a range of tailored polycyclic aromatic hydrocarbons and graphene fragments.

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