Hydrocarbonylation of alkenes with carboxylic acids in synthesis of carboxylic acid anhydrides is relatively less explored. We herein present a study and optimization of a palladium-catalyzed... Show moreHydrocarbonylation of alkenes with carboxylic acids in synthesis of carboxylic acid anhydrides is relatively less explored. We herein present a study and optimization of a palladium-catalyzed hydrocarbonylation reaction of alkenes using carboxylic acids as the nucleophile, by which acid anhydrides can be obtained in moderate to excellent yields under mild conditions. Further, we have developed a method to synthesize symmetric acid anhydrides by in situ generation of carboxylic acids from the alkene itself, thereby eliminating the need of the corresponding pre synthesized Cn+1 carboxylic acid. The obtained anhydrides from the catalysis can be converted to (primary) amides, thioesters, esters or ketones via simple one-pot derivatization reactions. Following the establishment of the concept, we applied it in the synthesis of cyclic anhydrides from biobased sources such as pentenoic acid. A study on the regioselectivity demonstrated the different catalytic conditions that assisted in the formation of five-, six- or seven- membered cyclic anhydrides from pentenoic acid; with a major interest towards the formation of the seven-membered ring - a potential intermediate in the synthesis of caprolactam for nylon-6 production. Show less
Kloos, D.; Derks, R.J.E.; Wijtmans, M.; Lingeman, H.; Mayboroda, O.A.; Deelder, A.M.; ... ; Giera, M. 2012
