Date of Award
Spring 2016
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Yi, Chae S.
Second Advisor
Fiedler, Adam
Third Advisor
Dockendorff, Christopher
Abstract
Etherification of alcohols is one of the most fundamental transformations in organic synthesis. Williamson ether synthesis is the most well-known synthetic method of unsymmetrical ether synthesis which is still being used in both industrial and academic laboratories. We have developed a novel catalytic etherification reaction using two different alcohols by using a well-defined cationic ruthenium catalyst. The reaction scope as well as the mechanistic study of the reaction are described.Hydroacylation is considered to be a powerful synthetic transformation for producing functionalized ketones from relatively simple olefin substrates. Despite remarkable progress in intra and intermolecular hydroacylations, the substrate scope of the reaction was limited to chelate assisted aldehydes and alkenes. We developed a highly regioselective intermolecular hydroacylation by using a well-defined cationic ruthenium catalyst. The reaction scope as well as the mechanistic study of the reaction are described.Transition metal catalyzed C(sp3)-H bond activation is highly challenging but very important in a number of catalytic reforming processes in the petroleum industries. Tandem reactions are a powerful strategy due to the reduction of work-up procedures and multiple purification steps. We developed a novel tandem catalytic reaction involving C(sp3)-H bond activation and functionalization by using a well-defined tetra ruthenium catalyst. The scope and synthetic utility of the tandem dehydrogenation-alkylation reaction are described.