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Development and Mechanistic Investigation of Potassium Tert-Butoxide Catalyzed C–H Silylation

Citation

Schuman, David Phillip (2020) Development and Mechanistic Investigation of Potassium Tert-Butoxide Catalyzed C–H Silylation. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/248y-cp18. https://resolver.caltech.edu/CaltechTHESIS:04132020-174738338

Abstract

The synthetic organic community has a long history of concurrent development of new methods, total syntheses, and mechanistic investigations. For example, new methods may allow the synthesis of previously inaccessible synthetic targets or a challenging transformation in a total synthesis may lead to the development of new reaction methods. Understanding the mechanism of a reaction may lead to the development of new methods or application in total synthesis. Historically, the Stoltz group has found great success focusing on the synergistic development of reaction methods, total synthesis, and mechanistic investigation. This thesis focuses on the mechanistic investigation of a novel method developed by our group and a number of new methods inspired by this better understanding of the reaction mechanism.

Initially, an overview of transition-metal-free, catalytic C–H silylation reactions is presented. Next, a detailed mechanistic investigation into the KOt-Bu-catalyzed C–H silylation reaction of aromatic heterocycles is presented. This investigation covers a series of experimental, computational, and analytic techniques to probe possible radical or ionic reaction mechanisms. The development of a number of new methods is presented including the catalytic trimethylsilylation of aromatic heterocycles and catalytic silylation of terminal alkynes.

Finally, the current progress of our efforts toward the total synthesis of the natural product illisimonin A are presented.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Catalyst, catalysis, heterocycle, silylation, mechanism
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Stoltz, Brian M.
Thesis Committee:
  • Reisman, Sarah E. (chair)
  • Agapie, Theodor
  • Grubbs, Robert H.
  • Stoltz, Brian M.
Defense Date:20 March 2020
Record Number:CaltechTHESIS:04132020-174738338
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:04132020-174738338
DOI:10.7907/248y-cp18
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.6b13031DOIArticle adapted for Chapter 2.
https://doi.org/10.1021/jacs.6b13032DOIArticle adapted for Appendix 3.
https://doi.org/10.1021/jacs.6b12114DOIArticle adapted for Appendix 6.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13674
Collection:CaltechTHESIS
Deposited By: David Schuman
Deposited On:17 Apr 2020 00:15
Last Modified:16 Oct 2020 15:48

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