Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation. Issue 40 (28th August 2019)

• Record Type: Journal Article
• Authors: Sang, Rui; Kucmierczyk, Peter; Dühren, Ricarda; Razzaq, Rauf; Dong, Kaiwu; Liu, Jie; Franke, Robert; Jackstell, Ralf; Beller, Matthias
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 40(2019)
• Page Start: 14365
• Page End: 14373
• Publication Date: 2019-08-28
• Subjects: carboxylic acids -- industrial chemistry -- ligand design -- olefins -- palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201908451
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The synthesis of carboxylic acids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers, cosmetics, pharmaceuticals, agrochemicals, and other manufactured chemicals. Although hydroxycarbonylations of olefins have been known for more than 60 years, currently known catalyst systems for this transformation do not fulfill industrial requirements, for example, stability. Presented herein for the first time is an aqueous‐phase protocol that allows conversion of various olefins, including sterically hindered and demanding tetra‐, tri‐, and 1, 1‐disubstituted systems, as well as terminal alkenes, into the corresponding carboxylic acids in excellent yields. The outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key‐to‐success is the use of a built‐in‐base ligand under acidic aqueous conditions. This catalytic system is expected to provide a basis for new cost‐competitive processes for the industrial production of carboxylic acids. Abstract : The outstanding stability of the pictured catalyst system (>25 recycling runs in 32 days without measurable loss of activity), which is unprecedented for Pd‐catalyzed hydroxycarbonylations, is showcased in the preparation of an industrially relevant fatty acid. Because of its efficiency and generality, it provides a basis for new cost‐competitive processes for the industrial production of carboxylic acids.