Citation
Williams, Chloe Gabrielle (2023) Development of Selective Carbon–Carbon Bond-Forming Reactions of Vinyl Carbocations. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/rkge-pz74. https://resolver.caltech.edu/CaltechTHESIS:06052023-155701672
Abstract
Carbocationic intermediates play an important role in the construction of complex molecules, from biosynthetic pathways in nature to the synthesis of natural products by organic chemists. Herein, a brief introduction that surveys C–C bond forming reactions of vinyl carbocations is highlighted. The discussion of experimental work commences with the development of a main group-catalyzed approach towards accessing vinylated esters through the trapping of vinyl carbocations with silyl ketene acetals. Next, a Claisen-type rearrangement is discussed, which is a result of trapping vinyl carbocations with allyl ethers to form an allyl vinyl oxonium intermediate in situ that can subsequently rearrange. Finally, the last method that is highlighted includes the development of an asymmetric C–H insertion reaction of vinyl carbocations to forge bicyclic products in a highly enantioselective fashion.
| Item Type: | Thesis (Dissertation (Ph.D.)) | |||||||||
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| Subject Keywords: | main group catalysis, asymmetric catalysis | |||||||||
| Degree Grantor: | California Institute of Technology | |||||||||
| Division: | Chemistry and Chemical Engineering | |||||||||
| Major Option: | Chemistry | |||||||||
| Thesis Availability: | Public (worldwide access) | |||||||||
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| Defense Date: | 31 May 2023 | |||||||||
| Record Number: | CaltechTHESIS:06052023-155701672 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechTHESIS:06052023-155701672 | |||||||||
| DOI: | 10.7907/rkge-pz74 | |||||||||
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| Default Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 16084 | |||||||||
| Collection: | CaltechTHESIS | |||||||||
| Deposited By: | Chloe Williams | |||||||||
| Deposited On: | 08 Jun 2023 15:07 | |||||||||
| Last Modified: | 08 Nov 2023 00:49 |
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