PhD defence

Palladium-catalyzed carbonylative synthesis of carboxylic acid anhydrides from alkenes

• A. Ramakrishnan

Date

Tuesday 19 December 2023

Time

10:00 - 10:45 hour

Address

Academy Building
Rapenburg 73
2311 GJ Leiden

Supervisor(s)

• Prof.dr. E. Bouwman
• dr. D.G.H. Hetterscheid

Summary

Hydrocarbonylation of alkenes with carboxylic acids to synthesize 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 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 assist 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.

PhD dissertations

Approximately one week after the defence, PhD dissertations by Leiden PhD students are available digitally through the Leiden Repository, that offers free access to these PhD dissertations. Please note that in some cases a dissertation may be under embargo temporarily and access to its full-text version will only be granted later.

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