ChemSusChem. 2022 Jun 12. doi: 10.1002/cssc.202201006. Online ahead of print.
The synthesis of acetic acid by formal isomerization of methyl formate (MF) was investigated using molecular catalysts. The base-catalyzed decarbonylation of MF, yielding CO and methanol in-situ , was integrated with their palladium-catalyzed recombination for the synthesis of acetic acid and methyl acetate in a one pot reaction . The complex [Pd(Cl) 2 (dppe)] (dppe = 1,2-bis(diphenylphosphino)-ethane) in combination with NaI as iodide source and NaOMe as base were identified as promising molecular components to enable the overall conversion. Sequential application of the statistical methods DoE (design of experiments) and simplex optimization was used in combination with thermodynamic analysis of the competing reaction pathways for experimental planning and data analysis. Starting from a proof-of-principle with a turnover number (TON) of 11, the catalytic system could thus be elaborated to allow quantitative conversion of MF with a TON of 43,000 whereby a yield of 83% of acetate groups and a yield of 74% for free acetic acid was obtained.