Palladium complex catalysis with methanol

Monohgated oxazolines derived from commercially available 2-ethyl-2-oxazoUne can form trans-square-planar palladium complexes by simple treatment of this ligand with inorganic palladium salts in methanolic solutions (Scheme 6.15) [72]. The catalysis, when performed in pyrrolidine, gave a yield of 32%, which corresponded to a TON of 190. The Sonogashira reaction was carried out under aerobic conditions with no precautions to exclude moisture from the solvent or substrates. 

Alkenes and/or alkynes can be dimerized, telomerized, and polymerized under palladium-catalysis. In an effort to copolymerize polar co-monomers, Johnson et al. investigated catalysts based upon palladium. These catalysts were referred to as postmetallocene catalysts. They were based upon complexes bearing bulky, neutral, alpha-diimine (or diketimine) ligands. They have been commercialized as DuPont s Versipol olefin polymerization system. The commercial synthesis of 1-octene (starting in 2007) is a palladium-catalyzed telomerization of butadiene with methanol. ... 

Conversion of ethylene to acetaldehyde with a soluble palladium complex was one of the early applications of homogeneous catalysis. As most of the acetic acid-manufacmring processes were based on acetaldehyde oxidation, the easy conversion of ethylene to acetaldehyde by the Wacker process was historically a significant discovery. With the advent of the methanol carbonylation process for the manufacture of acetic acid, the industrial importance of the Wacker process has diminished. 

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