Physical Sciences and Mathematics Commons^™

Investigation Of Catalytic Oxidation And Coupling Reactions On Gold, Palladium, And Gold-Palladium Alloys, Theodore Douglas Thuening

Theses and Dissertations

Polyvinyl acetate is a common adhesive and additive to emulsion-based paints produced in the millions of tons per year through the palladium catalyzed coupling of ethylene and acetic acid. Understanding the reaction mechanism and kinetics is integral to designing a more efficient catalyst through an increase in activity, selectivity, or both. It has been shown that selectivity for the vinyl acetate monomer (VAM) reaction increases to ~94% upon alloying palladium with gold compared to palladium alone (~80% selective).

The characterization of the VAM formation reaction on Pd(111) and Au/Pd(111) single crystal alloys has been extensively studied, but it has been …

I. Studies On The Organocatalytic Formation Of Quaternary Stereocenters. Ii. Studies On The Claisen Rearrangement As A Route To Quaternary Stereocenters. Iii. Asymmetric Synthesis Of Aldehydes Bearing Quaternary Carbon Centers Via The Decarboxylative Asymmetric Allylic Alkylation, Eduardo Alberch

Theses and Dissertations

The asymmetric synthesis of all carbon quaternary stereocenters poses a particular challenge due to the steric congestion inherent in the formation of such centers and has been the object of intense research these last 20-30 years. However, the amount of literature for the synthesis of aldehydes bearing quaternary stereocenters via enolate type chemistry is much more limited due to problems associated with the alkylation of such substrates including such types as Cannizzaro and Tischenko related reactions or self aldol condensations. The formation of aldehydes with quaternary stereocenters via use of enolate equivalents such as the DAAA (decarboxylative asymmetric allylic alkylation) …