Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation. (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. Volume 131:Number 40(2019)
• Page Start: 14503
• Page End: 14511
• Publication Date: 2019-08-28
• Subjects: Carbonsäuren -- Industrielle Chemie -- Ligandendesign -- Olefine -- Palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201908451
• Languages: English
• ISSNs: 0044-8249

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 : Die herausragende Stabilität des gezeigten Katalysatorsystems (>25 Recycling‐Durchläufe in 32 Tagen ohne messbaren Aktivitätsverlust) ist beispiellos für Pd‐katalysierte Hydroxycarbonylierungen; dies wurde beispielhaft anhand der Herstellung einer industriell relevanten Fettsäure demonstriert. Dank seiner Effizienz und Allgemeingültigkeit bietet es eine Basis für neue, wettbewerbsfähige Prozesse zur industriellen Carbonsäureproduktion.