Asymmetric Carbon-Carbon Bond Formation Via 3,3'-Reductive Elimination of Allyl Palladium Complexes

Abstract

This dissertation describes the development of two enantioselective methods of carbon-carbon bond formation. Chapter one discusses the development of an enantioselective Pd(0)-catalyzed conjugate addition of allylboronic acid pinacol ester to α,β-unsaturated methylidene ketones. Utilizing the same rationale for regio- and enantiocontrol as in the related enantioselective conjugate allylation of arylidene ketones, this method addresses the gap in technology by expanding the scope of the reaction to include alkyl-substituted enones. Chapter two examines the coupling of allyl electrophiles and allyl metal reagents. With computational insight into the reaction mechanism, a catalyst system was designed to control regioselectivity and enantioselectivity. Isotope labeling studies were carried out to probe the mechanism of the transformation. The reaction also proves to be diastereoselective when a substituted allyl boron reagent is employed.