A direct, catalytic protodecarboxylation of primary, secondary, and tertiary carboxylic acids is reported. The catalytic system consists of a visible light active acridinium photooxidant with phenyldisulfide acting as a redox-active co-catalyst. Substoichiometric quantites of Hunig’s base are used to reveal the carboxylate. Use of trifluoroethanol (TFE) as a solvent has allowed for significant improvements in substrate compatibilities, as the method reported is not limited to carboxylic acids bearing alpha heteroatoms or phenyl substitution. This method has been applied to the direct double decarboxylation of malonic acid derivatives, which allows for the convenient use of dimethyl malonate as a methylene synthon. Several mechanistic studies were carried out in order to better understand the improved reactivity in TFE.

Protodecarboxylation of unstablized carboxylic acids and malonic acid derivatives through photoredox catalysis

249th National Meeting (2015)

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