Palladium-catalyzed cross-coupling reactions with propargyl electrophiles typically form the allenyl or bis-addition products. Selectivity for the propargyl or 1,3-dienyl products is extremely rare. Previous work in our lab has shown that propargylic carbonates can be reacted with diaryl acetonitrile pronucleophiles in the presence of palladium and phosphorus ligands to selectively form either the propargyl or 1,3-dienyl diarylmethane product. Building upon these results, propargyl carbonates were reacted with various 1,3-dicarbonyl compounds. The formation of either 1,3-dienyl or terminal propargylated products is proposed to arise from a deviation in the reaction mechanism depending on the pKa of the 1,3-dicarbonyl starting material. Dienyl products were then reacted with N-Phenylmaleimide to provide Diels-Alder adducts in good yields.

Decarboxylative dienylation and propargylation of 1,3-dicarbonyl compounds

ACS Spring Meeting 2021

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