Carboxylic acids as directing groups for intramolecular catalytic oxidation of unactivated C(sp3)-H bonds with bioinspired catalysts

In this thesis we developed a protocol for the intramolecular oxidation of prochiral secondary C-H bonds in which carboxylic acids, acting as directing groups for the oxidant species, promoted a highly site-selective and lactone product chemoselective oxidation. The versatility and general applicability of the reaction is witnessed by the successful oxidation of 25 substrates involved in this study, of note, even at strong primary C-H bonds.Rational catalyst design and judicious choice of the substrates enabled the first example of non-enzymatic, chiral C(sp3)-O bond-forming catalytic reaction from an unactivated C-H bond. Rationally designed experiments unveiled the single contribution of reagents and solvents to the reaction efficiency. Interestingly, isotopic labelling experiments bring to light a carboxylate rebound pathway, unprecedented in the mechanistic landscape of Fe and Mn bioinspired oxidations ​
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