Leiden University Scholarly Publications

Persistent URL of this record https://hdl.handle.net/1887/3674100

In Collections

This item can be found in the following collections:

Ramakrishnan, A. (2023)

Palladium-catalyzed carbonylative synthesis of carboxylic acid anhydrides from Alkenes

Doctoral Thesis
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 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...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
Homogenous Catalysis
Carboxylic acids
Carboxylic acid anhydrides
Alkenes
Carbonylation
All authors
Ramakrishnan, A.
Supervisor
Bouwman, E.; Hetterscheid, D.G.H.
Committee
Ubbink, M.; Bonnet, S.A.; Beller, M.; Fernández Ibánez, M.A.; Limburg, B.
Qualification
Doctor (dr.)
Awarding Institution
Leiden Institute of Chemistry (LIC), Faculty of Science, Leiden University
Date
2023-12-19