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Title: Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
Authors: Nielsen, Daniel
Advisors: Doyle, Abigail G
Contributors: Chemistry Department
Keywords: aziridine
C-N bond activation
C-O bond activation
cross coupling
Subjects: Organic chemistry
Issue Date: 2013
Publisher: Princeton, NJ : Princeton University
Abstract: Epoxides and aziridines are invaluable substrates for complex molecule synthesis due to their accessibility and proclivity toward ring opening. Generally, C-C bond formation with these substrates is uncatalyzed and requires either harsh stoichiometric organometallic reagents or a narrow set of stabilized carbanions, thereby limiting the generality of these transformations. To address these drawbacks, we have investigated the transition metal-catalyzed cross coupling of epoxides and aziridines. Conditions for the coupling of styrenyl epoxides with boronic acids were developed; a variety of alpha-substituted alcohols are generated with good reaction efficiency. Mechanistic studies support a multi-catalytic sequence involving Csp3-O bond activation. This methodology was extended to include the cross coupling of simple aliphatic aziridines with zinc nucleophiles. Crucial to the success of this transformation was the development of a novel protecting group capable of coordinating the catalyst, activating the aziridine toward oxidative addition, and assisting in reductive elimination. This transformation represents the first use of a non-benzylic or allylic Csp3-N bond as an electrophile in a catalytic cross-coupling reaction and affords medicinally relevant beta-substituted amines.
Alternate format: The Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

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