The Hydroformylation Reaction: from Covalent to Supramolecular Approaches and Operando Kinetic Studies

The hydroformylation reaction is one of the most important examples of homogeneous catalysis applied at the industrial scale. The potential of this transformation is recognized as it enables the transformation of inexpensive and easily available alkenes into functionalized organic molecules, which are relevant intermediates in the production of commodities and fine-chemistry products.

The main objective of the present doctoral thesis comprises the study of the hydroformylation reaction from different perspectives (i.e., from the methodological and mechanistic points of view) and the use of rhodium- and cobalt-based catalysts. The first part encompasses the design and synthesis of new supramolecularly regulated bisphosphine and bisphosphite ligands for the rhodium-catalyzed hydroformylation of 1,1’-disusbtituted allenes. In addition, the cobalt-catalyzed hydroformylation of aryl- and alkyl-substituted alkenes in presence of Xantphos as ligand was studied. In case of internal alkenes, a tandem isomerization-hydroformylation process occurs. This tandem reaction may be a valuable tool for the valorization of petroleum feedstock. Following our efforts in developing highly efficient supramolecular catalytic systems incorporating a distal regulation site, we focused our interest on the enantioselective hydroformylation of aryl vinyl ethers employing supramolecularly regulated rhodium-bisphosphite complexes. ¨This methodology allowed us for the preparation of advanced synthetic intermediates of agrochemicals. Finally, an experimental setup was designed and developed for the online reaction monitoring of the hydroformylation reaction under catalytic conditions. Variable Time Normalization Analysis (VTNA) was used as a visual kinetic analysis method to extract relevant kinetic information. The VTNA allowed for the removal of the induction period observed in the product formation, revealing a simple profile and a real first-order dependence on substrate and catalyst concentrations in the hydroformylation reaction.

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