Harnessing the Chirality of Phosphorus Compounds, from Catalysis to Application

Many bioactive molecules and essential building blocks of biological systems are chiral and contain phosphorus (P) in the oxidation state (V). Such compounds are ubiquitous in nature and pivotal for numerous biological processes such as membrane formation, cell replication, information (DNA, RNA), proper functioning of enzymes and proteins, glycolysis and energy metabolism. Moreover, phosphorus‒carbon- (P‒C)- and phosphorus‒nitrogen- (P‒N)-bonds belong to essential structural motifs in many functional materials, ligands in metal catalysis, pharmaceuticals, fertilizers, detergents and pesticides. Therefore, chiral phosphorus-containing compounds are interesting targets for applied research, but should be also considered when investigating the homochirality and origin of life.
Precisely these motivations spearheaded the work in this thesis, which revolves around the chirality of organophosphorus compounds. More specifically, it focusses on the development of new catalytic diastereoselective and enantioselective reactions to access P(V)-substituted substrates. Furthermore, the chiral products of these reactions and their ability to form aggregates were investigated, which led to observation of intriguing self-resolving properties. Moreover, this offered an attractive approach to enantioenrichment by phase-partitioning, which is often discussed in context of homochirality. Finally, the design of a new (asymmetric) autocatalytic reaction was attempted, which is considered to be an alternative pathway to obtain molecular single-handedness on Earth.