Herein we report the first examples of γ-arylation of esters. This work expands on palladium catalyzed α-arylation chemistry and extends it to the more challenging vinylogous variation at the γ-arylation position. γ-arylation has all of the difficulties of alpha arylation, in particular over-arylation. Added to this mix are concerns of regiochemistry when attempting arylation at the γ-position. Development of the methodology is presented as well as current scope and limitations of the disclosed methodology.<br/>For our first examples we chose derivatives of 4-methylcoumarin to investigate. Coumarins are well known for their antibiotic, antifungal, anti-inflammatory, and antiviral activities. Not only are coumarins biologically active, but they can also be utilized as additives in food and cosmetics, in the preparation of optical brighteners, in dispersed fluorescent, and laser dyes making this an attractive target. This method provides a simple route toward 7-methoxy-4-(aryl)methylcoumarins.

Palladium catalyzed mono-γ-arylation of 4-methylcoumarin

254th National Meeting (2017)

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