Investigations in asymmetric catalysis and applications to the synthesis of laulimalide

This thesis outlines the development and application of new methods in asymmetric catalysis. In principle, this development can occur in three major areas: the development of new catalytic methods, the design of new catalysts for existing methodology, and the application of asymmetric catalysis in synthetic chemistry. Each of these three major areas is exemplified in the three chapters of this thesis.; Chapter one highlights the design and synthesis of a novel class of chiral ligands that can be applied to asymmetric catalysis. This new class of chiral ligands relies on a planar-chiral [arene]Cr(CO)₃ complex as a scaffold for the development of a chiral phosphine complex. Unlike the vast majority of chiral phosphines, this family of chiral ligands contains only one basic phosphine residue. They are, therefore, tailor made for metal-catalyzed processes requiring only one phosphine ligand in the catalyst's ligand sphere.; Chapter two details the application of an asymmetric catalytic synthesis of β-lactones in the synthesis of laulimalide, a potent anti-tumor marine natural product. Beta-lactones were exploited in setting four stereocenters contained in the natural product.; Chapter three highlights the development of a McMurry pinacol coupling catalyzed by a titanium (IR) complex. Both aliphatic and aromatic aldehydes are reductively coupled to the corresponding diol using substoichiometric quantities of TiCl₃(THF)₃. Stoichiometric quantities of TMSCl and Zn or Mn allow for the regeneration of the Ti catalyst complex. At the onset of this investigation, a catalytic reductive coupling of two aldehydes to the corresponding diol had not been reported in the literature.