Organocatalytic Approaches to Asymmetric Oxidation

This work describes the development of enantioselective oxidation reactions of carbonyl compounds using covalent organocatalysis. In the first part, asymmetric epoxidation of -branched ,beta-unsaturated aldehydes with aqueous hydrogen peroxide is presented. An exceptionally synergistic combination of a primary cinchona alkaloid-derived amine and a chiral BINOL-derived phosphoric acid was found to promote the reaction with excellent enantiocontrol for a wide variety of ,beta-disubstituted and -monosubstituted enals. Conformational analysis of catalytically relevant intermediates using NMR and computational techniques enabled the rationalization of the absolute stereochemistry of products. The second part of this book describes a highly efficient direct catalytic asymmetric -benzoyloxylation of cyclic ketones. The same primary amine paired with an inorganic acid was found to be an effective catalyst for a wide range of substrates. The methodology was applied to the first asymmetric synthesis of (+)-2beta,4-dihydroxy-1,8-cineole, a predicted terpenoid metabolite in mammals.

Autorentext

Olga Schöne was born Russia and educated in Russia, Canada and Germany. She obtained her PhD at the Max-Planck-Institute for Coal Research in 2012, and moved to the Ludwig Maximilians University in Munich for a postdoctoral stay in natural product synthesis. In 2014, she moved again to Austria to begin her R&D job in the pharmaceutical industry.