Palladium-catalyzed oxidative heteroarylation of an olefin has been extensively studied as a method to rapidly increase molecular complexity during synthesis. Mechanistic studies have suggested that when high oxidation state palladium is used the reaction proceeds via C-H activation of the aromatic ring. While investigating an intramolecular variant of the oxyarylation reaction with 2,2-diaryl-4-pentenoic acids in the presence of a palladium catalyst and an external oxidant, we observed an interesting substrate dependent rearrangement of the backbone aromatic ring that competes with the direct C-H insertion. The ratio of products is highly dependent on the position of electron-donating groups on the aromatic rings. Herein, we report the optimization of this novel transformation and the effects of the aromatic substituents. We will also discuss our mechanistic investigations into the reaction to explain the observed divergence in reactivity.

Substituent effects in intramolecular palladium-catalyzed oxyarylation reactions

2019 Spring National Meeting

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