Thesis presented December 15, 2016
Abstract:
A lot of organic chemicals are synthesized via oxidation steps. That means the use of harsh conditions, toxic oxidants like osmium tetraoxide and sometimes asymmetric catalysts. On the way of the environment protection, there is a need for eco-friendly processes based on green chemistry. In this goal, my PhD work targets the development of new catalysts mixing an inorganic moiety with a protein called artificial metalloenzymes. Artificial metalloenzymes are able to catalyze oxidation reactions under mild conditions, with smooth oxidants and water as solvent. In a first part, I describe the design and characterization of a new artificial metalloenzyme based on a ruthenium scorpionate and the protein NikA from
E. coli. Its reactivity has then been studied showing an unusual reactivity and transforming a series of alkenes in chlorohydrins with high chemio- and regio-selectivities. Enantioselectivity has been studied on a range of substrates and protein homologs. In a second part, I describe the design and characterization of a new iron and NikA artificial metalloenzyme. Its reactivity has been tested with oxygen as the oxidant under reducing conditions. Its ability to transfer an oxygen atom to a substrate has been demonstrated with aromatic alkenes under photocatalysis.
Keywords:
catalysis, artificial metalloenzyme, activation of molecular oxygen