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Investigation of Wacker-type oxidation reactions using palladium(II) catalysts and tert-butyl hydroperoxide Calum Maguire (24169359) PUREID: 619397702 oxidation palladium catalysis peroxide Wacker inorganic chemistry catalysis hexafluoroisopropanol tert-butyl hydroperoxide The oxidation of alkenes to ketones, is a useful reaction that has applications in complex organic synthesis. 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. Applicability to complex organic synthesis, by oxidation of multi-functionalised substrates has also highlighted the synthetic utility of the system.<br><br>Finally, Pd(II) carboxylate complexes have been studied as more accessible catalysts as these can be synthesised from commercially available Pd(II) salts. HFIP was found to be essential in promoting the activity of these complexes for TBHP Wacker oxidations. A range of challenging model substrates, such as styrene, aliphatic substrates and allylic ethers could be oxidised to give the products in high yield and selectivity, using low catalyst loadings.<br> 2026-10-01T16:29:59Z Text Thesis 10.17034/32640573.v1 https://figshare.com/articles/thesis/Investigation_of_Wacker-type_oxidation_reactions_using_palladium_II_catalysts_and_tert-butyl_hydroperoxide/32640573 All Rights Reserved