Palladium-catalyzed olefin dioxygenation is a powerful tool in the generation of complex and valuable substrates, one which may become complimentary to the well known Sharpless dihydroxylation. In this work the mechanism of this transformation is examined via reaction kinetics and Hammett studies, which corroborate a PdII/IV catalytic cycle and suggest that the rate determining step is the oxidation of PdII to PdIV. Olefin dioxygenation was also found to proceed in the presence of catalytic quantities of BF3•OEt2 or triflic acid, with stoichiometric hypervalent iodine oxidant and an acetic acid solvent. Furthermore, asymmetric variants of intramolecular palladium-catalyzed olefin dioxygenation were also investigated, which resulted in the formation of tetrahydrofuran products in up to 36% ee. Next, chelate-assisted C–H bond functionalization of indoles at the C7 position and of carbazoles at the C1 position was investigated with a variety of arylation, halogenation and oxygenation techniques. Lastly, our efforts towards the synthesis of a mono-phosphine based [5]helicene ligand via olefin metathesis and photocyclization strategies will be discussed.

Palladium-catalyzed olefin dioxygenation is a powerful tool in the generation of complex and valuable substrates, one which may become complimentary to the well known Sharpless dihydroxylation. In this work the mechanism of this transformation is examined via reaction kinetics and Hammett studies, which corroborate a PdII/IV catalytic cycle and suggest that the rate determining step is the oxidation of PdII to PdIV. Olefin dioxygenation was also found to proceed in the presence of catalytic quantities of BF3•OEt2 or triflic acid, with stoichiometric hypervalent iodine oxidant and an acetic acid solvent. Furthermore, asymmetric variants of intramolecular palladium-catalyzed olefin dioxygenation were also investigated, which resulted in the formation of tetrahydrofuran products in up to 36% ee. Next, chelate-assisted C–H bond functionalization of indoles at the C7 position and of carbazoles at the C1 position was investigated with a variety of arylation, halogenation and oxygenation techniques. Lastly, our efforts towards the synthesis of a mono-phosphine based [5]helicene ligand via olefin metathesis and photocyclization strategies will be discussed.