Investigations on the catalytic carboxylation of olefins with CO2 towards α, β-unsaturated carboxylic acid salts

• Verfasst von: Jevtovikj, Ivana [VerfasserIn]
• Verfasst von: Manzini, Simone [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Schaub, Thomas [VerfasserIn]
• Titel: Investigations on the catalytic carboxylation of olefins with CO2 towards α, β-unsaturated carboxylic acid salts
• Titelzusatz: characterization of intermediates and ligands as well as substrate effects
• Verf.angabe: Ivana Jevtovikj, Simone Manzini, Matthias Hanauer, Frank Rominger and Thomas Schaub
• E-Jahr: 2015
• Jahr: 05 May 2015
• Umfang: 12 S.
• Fussnoten: Im Titel ist die 2 bei CO tiefgestellt ; Im Titel werden "alpha" und "beta" als griechische Buchstaben dargestellt ; Gesehen am 09.06.2020
• Titel Quelle: Enthalten in: Dalton transactions
• Ort Quelle: London : Soc., 1972
• Jahr Quelle: 2015
• Band/Heft Quelle: 44(2015), 24, Seite 11083-11094
• ISSN Quelle: 1477-9234
• DOI: doi:10.1039/C5DT01040C
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1700199714

Abstract

The carboxylation of olefins beyond ethylene towards α,β-unsaturated carboxylic acid salts and a detailed investigation on the critical steps in the catalysis are reported. The influence of two chelating phosphine ligands and several olefins on the elemental steps of the catalysis is shown. The work focusses on the formation of intermediate olefin complexes, lactone formation and base induced elimination of the lactone. The direct carboxylation of olefins is possible using nickel catalysts, which opens a new route towards the desired α,β-unsaturated carboxylic acid salts. The reaction works particularly well for 1,3-dienes and proceeds via the formation of allyl-carboxylates. The ability to form such allyl-type lactone complexes seems in this case to be the most challenging step towards satisfactory turnover numbers.