Palladium‐Catalyzed Carbonylation of sec‐ and tert‐Alcohols

• Published in: Angewandte Chemie International Edition Vol. 56; no. 22; pp. 6203 - 6207
• Main Authors: Dong, Kaiwu, Sang, Rui, Liu, Jie, Razzaq, Rauf, Franke, Robert, Jackstell, Ralf, Beller, Matthias
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 22.05.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alcohol; Alcohols; carbonylation; Carbonyls; catalysis; Catalysts; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Esters; Palladium; Physical Sciences; Science & Technology; OXIDATIVE CARBONYLATION; ALKOXYCARBONYLATION; esters; BUTYL ALCOHOL; COMPLEXES; catalysis; alcohols; HIGHLY SELECTIVE FORMATION; ALLYLIC ALCOHOLS; SATURATED ALCOHOLS; palladium; REGIOSELECTIVE CATALYSTS; LIGAND; carbonylation; HYDROXYCARBONYLATION
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201701950

A general palladium‐catalyzed synthesis of linear esters directly from sec‐ and tert‐alcohols is described. Compared to the classic Koch–Haaf reaction, which leads to branched products, this new transformation gives the corresponding linear esters in high yields and selectivity. Key for this protocol is the use of an advanced palladium catalyst system with L2 (pytbpx) as the ligand. A variety of aliphatic and benzylic alcohols can be directly used and the catalyst efficiency for the benchmark reaction is outstanding (turnover number up to 89 000). Ligands with built‐in function make possible the first general carbonylation of tert‐ and sec‐alcohols to give the linear esters. The reactions complement the classic Koch–Haaf carbonylation. A variety of aliphatic and benzylic alcohols can be directly used.