Investigations into dirhodium catalyst development and silver catalyzed decomposition of donor/acceptor substituted carbenoids
Thompson, Janelle Leigh
MetadataShow full item record
This thesis broadly discusses investigations into dirhodium, silver and ruthenium catalyst development and how they interact with donor/acceptor substituted diazoacetate compounds. The first chapter discusses the development of novel high symmetry dirhodium catalysts for carbenoid reactions. During the course of these studies, the overarching focus has been on the design principle based around the concept of identical ligands of high symmetry ( C 1 ) arranged around a metal core to create a complex of overall higher symmetry ( D 2 ). The design and synthesis of novel bridged dirhodium tetracarboxylate catalysts has been investigated as well as the ability of these complexes to induce stereocontrol into standard cyclopropanation reactions. As an extension of this concept, ligands of even higher symmetry ( C 2 ) were utilized to synthesize chiral catalysts of D 4 symmetry. Chapter two will investigate the use of silver hexafluoroantimonate (AgSbF 6 ) to catalyze the decomposition of methyl phenyldiazoacetate and methyl phenylvinyldiazoacetate. The resulting silver carbenoids were found to be capable of highly diastereoselective cyclopropanation reactions and they display a very different reactivity profile compared to traditional rhodium catalysts. The development of this methodology and the comparison to rhodium acetate-catalyzed reactions is discussed. Chapter three studies the use of alternative dimetallic catalysts for the decomposition of donor/acceptor substituted diazoacetate compounds. The catalysts used have been generously made and donated by two groups at The State University of New York at Albany. There are two types of catalysts used and thus, the chapter is divided into two distinct sections. The first section is on the unique synthesis of diruthenium catalysts made by the research group of Prof. Marina Petrukhina and the work that has been done with these complexes in O-H insertion and the anomalous vinylogous reactivity these catalysts display. The second part of this chapter deals with mixed heterobimetallic rhodium-bismuth catalyst made by researchers in Prof. Evgeny V. Dikarev's laboratory. These catalysts display reactivity similar to that of rhodium acetate and other achiral dirhodium tetracarboxylate catalysts despite having only half of an active catalytic center present.