Investigation of Wacker-type oxidation reactions using palladium(II) catalysts and tert-butyl hydroperoxide

Traditional aerobic methods with palladium catalysts (Tsuji-Wacker conditions) suffer from several disadvantages, such as high catalyst loadings and poor product selectivity. The use of the organic peroxide, tert-butyl hydroperoxide (TBHP) is a useful alternative to hard aerobic conditions, but is less-well studied.

Solvent choice can influence these reactions and it has been found that hexafluoroisopropanol (HFIP) can enhance the performance.<br><br>The work in this thesis examines using TBHP as an oxidant in Wacker-type oxidations using ligated Pd(II) complexes. Cationic Pd(II) complexes were investigated and efficient catalysis is possible when used in the presence of HFIP. The role of HFIP and additional aspects of the optimised conditions, including solvent and oxidant choice have been investigated.<br><br>These dicationic complexes have also been applied to challenging substrates, such as allylic ethers and were found to be effective in their conversion to the corresponding methyl ketone products.