American Chemical Society
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Palladium-Catalyzed Alkylation of Aryl C−H Bonds with sp3 Organotin Reagents Using Benzoquinone as a Crucial Promoter

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journal contribution
posted on 2006-01-11, 00:00 authored by Xiao Chen, Jiao-Jie Li, Xue-Shi Hao, Charles E. Goodhue, Jin-Quan Yu
The combination of directed C−H activation, batch-wise addition of tetraalkyltin reagents, and rate enhancement by benzoquinone and microwave irradiation provides a promising strategy for the direct coupling of C−H bonds with organometallic reagents. A variety of tetraalkyltins were coupled to C−H bonds to give the alkylated products in good yields by using 5 mol % Pd(OAc)2 as the catalyst. Benzoquinone was shown to be essential for the C−H activation when substrates containing non-π-conjugated chelating groups are used. Monitoring the formation and reductive elimination of the Pd(Ar)(Me)L2 complex also revealed that benzoquinone promotes the reductive elimination step. Microwave irradiation enhances the reaction rate drastically. The versatility of this protocol was demonstrated by using substrates containing either oxazoline or pyridine as directing groups.