Chiral N-Heterocyclic Carbene Ligands: Enhancing Nickel-Catalyzed Asymmetric Syntheses

N-Heterocyclic carbenes (NHCs) are preferred ligands in numerous transformations involving various transition metals. Despite their broad utility, the availability of chiral NHCs for asymmetric catalysis is limited. However, a chiral version of the widely utilized IPr ligand could significantly enhance asymmetric transformation capabilities. This thesis details the development and further derivatization of chiral NHC ligands that are analogues of IPr. It explores their effectiveness in nickel-catalyzed enantioselective transformations, showcasing their considerable potential to improve various asymmetric synthetic processes. We introduce a novel Ni(0)NHC catalyst that efficiently alpha-allylates ketones with non-conjugated dienes, creating vicinal stereogenic centers with high diastereoselectivity and enantioselectivity. This catalyst activates alpha-hydrogens and transfers them to olefin acceptors. Computational studies show it facilitates LLHT processes, offering a sustainable approach to synthesizing valuable chiral building blocks. The use of a chiral Ni(0)NHC complex, featuring an electronically deficient chiral sidearm, is essential for synthesizing privileged chiral spirocyclic materials. This process employs an enantioselective [2+2+2] cycloaddition via a hetero coupling mechanism, offering significant opportunities for developing useful chiral materials.