Migratory Decarboxylative Coupling of Coumarins: Synthetic and Mechanistic Aspects

Authors


  • This work was supported by the National Institute of General Medical Sciences (NIGMS 1R01M079644).

Abstract

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On the move: Decarboxylative coupling of allyl 4-methyl-3-carboxycoumarins provides the products of γ-allylation of the methyl group rather than the typical regiospecific α-allylation. Mechanistic studies show that intramolecular proton transfer from the 4-methyl group to the 3-carboxylate allows allylation of the remote methyl group. The resulting 4-butenyl-3-carboxyl coumarin undergoes Pd0-catalyzed decarboxylation to provide the observed products (see scheme).

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