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Development of Sc(III)-catalyzed Homolog... - Document (12 M) |
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| Author |
Moebius, David Charles |
| Title |
Development of Sc(III)-catalyzed Homologation of Ketones by Non-stabilized Diazomethanes |
| Date created |
2011 |
| Abstract |
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. |
| Use Restrictions |
I hereby allow Boston College to include and preserve my dissertation/thesis in electronic form in the Boston College Institutional Repository, which shall include the right to publicly post my dissertation/thesis on the World Wide Web. I will retain copyright ownership, but I grant to Boston College the non-exclusive right to copy, distribute, and publicly display my dissertation/thesis in any form as may be necessary or convenient in the future as file formats, storage media, and distribution mechanisms evolve. |
| Subject |
catalysis |
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enantioselective |
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homologation |
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insertion |
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scandium |
| Publisher |
Boston College |
| Link to Item |
2345/2169 |
| Thesis Advisor |
Kingsbury, Jason S. |
| Degree Name |
PhD |
| Degree Grantor |
Boston College. Graduate School of Arts & Sciences. |
| Sys. No. |
000011855 |
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