Publication
N-Heterocyclic carbenes (NHCs) are privileged ligands in catalysis and especially for asymmetric transformations. Cyclic Alkyl Amino Carbenes (CAACs) are NHCs analogs displaying unique steric and electronic features. While CAAC organometallic complexes were reported to be competent in several unprecedented catalytic transformations, their applications in asymmetric catalysis remain extremely scarce. The development of a streamlined, robust and scalable synthetic route to access a modular family of chiral CAAC precursors and their downstream transition metal complexes is detailed in this thesis. The alteration of the ligand structure was thoroughly investigated, exploring the impact of chiral nitrogen substituents, chiral quaternary carbon adjacent to the carbene center as well as the elusive effect of backbone chirality. The prepared chiral CAAC transition metal complexes were assessed in a set of benchmark asymmetric catalytic transformations. Notably, an asymmetric conjugate borylation (ACB) reaction was extensively evaluated with the library of CAAC copper complexes, highlighting the crucial impact of the ligand evolution. The final introduction of a chiral backbone on the CAAC framework enabled to extend the scope of the ACB reaction, providing valuable quaternary organoboron product from various Michael acceptors. Finally, the ruthenium complexes were competent catalysts in an asymmetric ring closing metathesis transformation (ARCM).