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Development of Selective Carbon–Carbon Bond-Forming Reactions of Vinyl Carbocations


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.


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.))
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)
Research Advisor(s):
  • Nelson, Hosea M.
Thesis Committee:
  • Stoltz, Brian M. (chair)
  • Reisman, Sarah E.
  • See, Kimberly
  • Nelson, Hosea M.
Defense Date:31 May 2023
Record Number:CaltechTHESIS:06052023-155701672
Persistent URL:
Related URLs:
URLURL TypeDescription relevant to Chapter 2 relevant to Chapter 4
Williams, Chloe Gabrielle0000-0001-5090-8146
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16084
Deposited By: Chloe Williams
Deposited On:08 Jun 2023 15:07
Last Modified:13 May 2024 23:16

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