Enantioselective Isocyanoacetate Addition Reactions under Cooperative Base and Lewis Acid Catalysis. Enantiomerically pure substances with the capacity to simultaneously activate two reagents towards one another, offer numerous opportunities for the discovery of powerful, asymmetric bond forming reactions. When a compound possesses a combination of Brønsted (or Lewis) basic and Lewis acidic sites, has a well-defined chiral pocket constructed around a fairly rigid skeleton and appropriate distances between the two activating groups, the templating of a pronucleophile (NuH) and an electrophile via a ternary complex can lead to excellent levels of enantio- and diastereocontrol in efficient addition reactions at low catalyst loadings. The design and synthesis of new, readily accessible catalytic systems plays a pivotal role in this field of research allowing the discovery of useful synthetic pathways, rapid optimization of the ligand canopy and a better understanding of the mechanism and origins of stereocontrol. During this Fellowship we wish to develop new and synthetically powerful enantioselective inter- and intramolecular addition reaction of isocyanoacetate pronucleophiles under cooperative base and Lewis acid catalysis. In particular we wish to investigate the addition chemistry of imines and electron deficient double bonds, as well as intramolecular additions to pendant alkyne functionality, using novel aminophosphine precatalyst/transition metal ion combinations. Not only will these reactions constitute important developments in the field but the product structures are often biologically relevant, thus lending the chemistry to important synthetic applications.
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