Thesis advisor: Amir H. Hoveyda / In the course of a total synthesis of quebrachamine, we were faced with a late-stage enantioselective ring-closing metathesis that could not be promoted by any of the state-of-the-art chiral metathesis catalysts. To overcome this deficiency, we designed and developed a new class of catalysts based on mechanistic and theoretical principles. The new catalysts contain a stereogenic metal center and display unprecedented levels of reactivity and selectivity in enantioselective olefin metathesis, enabling us to complete our planned synthesis of quebrachamine. We have also discovered that non-productive metathesis reactions with stereogenic-at-Mo catalysts, generated and used in situ as a mixture of diastereomers, are crucial to the efficiency and enantioselectivity of the ring-closing metathesis reactions. Specifically, our studies have indicated that the two diastereomers of catalyst are in rapid equilibrium due to non-productive metathesis with ethylene, generated as the desired ring-closing reaction proceeds, thereby establishing a reaction manifold that is under Curtin-Hammett control. Finally, in our efforts to prepare air-stable precursors to stereogenic-at-Mo olefin metathesis catalysts, we have examined the addition of N,N-chelating ligands to Mo bis-pyrrolide complexes. Upon addition of 2,2′-bipyridyl to bis-dimethylpyrrolide Mo complexes, rather than the expected octahedral chelate, a five-coordinate monopyrrolide alkylidyne complex is generated. The complex displays good air-stability and efficiently serves as a precursor to stereogenic-at-Mo alkylidene catalysts; several alkylidyne complexes have been prepared. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
| Identifer | oai:union.ndltd.org:BOSTON/oai:dlib.bc.edu:bc-ir_101742 |
| Date | January 2010 |
| Creators | Malcolmson, Steven Joseph |
| 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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