Thesis advisor: Jason S. Kingsbury / The research of diazoalkanes dates back more than 100 years, yet a disproportionally small number of methods have been developed to utilize their unique reactivity patterns. This review seeks to analyze the history of methods used to synthesize diazoalkanes and to highlight the parallel growth in methods for their use in carbonyl expansion reactions. The development of Sc(III)-catalyzed ring expansion of cyclic ketones with non-stabilized diazoalkanes is presented. A brief overview of previous contributions to ring expansion methodology is presented in order to provide appropriate context to newly discovered methods. Our strategy for method development centered on several issues of practicality with regard to efficient synthesis of diazo nucleophiles as well as their safe handling. The results of this initial discovery laid the groundwork for the development of the first catalytic enantioselective ring expansion of cyclic ketones with diazoalkanes. As well as an improved methylene insertion reaction of silyl-substituted diazomethanes. / Thesis (PhD) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
| Identifer | oai:union.ndltd.org:BOSTON/oai:dlib.bc.edu:bc-ir_101506 |
| Date | January 2011 |
| Creators | Moebius, David Charles |
| Publisher | Boston College |
| Source Sets | Boston College |
| Language | English |
| Detected Language | English |
| Type | Text, thesis |
| Format | electronic, application/pdf |
| Rights | Copyright is held by the author, with all rights reserved, unless otherwise noted. |
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