Direct Decarboxylative Allylation and Arylation of Aliphatic Carboxylic Acids Using Flavin-Mediated Photoredox Catalysis

We describe herein a direct decarboxylative allylation of aliphatic carboxylic acids with allylsulfones using visible light and riboflavin tetraacetate (RFTA) as photocatalyst. The reaction proceeds at room temperature tolerating a wide range of functionalities, avoiding the use of external bases or additives. Mechanistic studies support that alkyl radicals are involved in the reaction and that a true photocatalytic cycle is operating. It is proposed that the carboxylic acid is deprotonated by [RFTA](center dot-), and the corresponding carboxylate acts as a reductive quencher of RFTA*, which after decarboxylation produces the alkyl radical. The methodology was adapted to prepare benzothiazoles substituted at C2, by reacting some carboxylic acids with 2-(phenylsulfonyl)benzothiazole. The number of carboxylic acids suitable for this arylation was lower than for the allylation and this different reactivity was briefly commented.