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Development of Stereoselective Iridium-Catalyzed Allylic Alkylation Methods

Citation

Shockley, Samantha Elizabeth (2018) Development of Stereoselective Iridium-Catalyzed Allylic Alkylation Methods. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/S93J-6P85. https://resolver.caltech.edu/CaltechTHESIS:05302018-124410879

Abstract

The Stoltz group, and moreover the synthetic community at large, has long been interested in the development of methods for the synthesis of enantioenriched all-carbon quaternary stereocenters. Historically, our group’s interest has centered on palladium-catalyzed allylic alkylation, though recently effort has moved to include the study of iridium catalysts. This thesis presents four related projects, all unified by the use of enantioselective iridium-catalyzed allylic alkylation to construct highly-congested C–C bonds.

First, the development of the first diastereo-, enantio-, and regioselective iridium-catalyzed allylic alkylation reaction of prochiral enolates to form vicinal tertiary and all-carbon quaternary stereodyads with alkyl-substituted allylic electrophiles is described. Next, the first enantioselective iridium-catalyzed allylic alkylation reaction of a masked acyl cyanide (MAC) nucleophile is presented, representing a rare example of umpolung strategy in iridium-catalyzed allylic alkylation. Additionally, the application of a MAC reagent in the first highly enantioselective iridium-catalyzed allylic alkylation to provide access to products bearing an allylic all-carbon quaternary stereocenter is detailed. The use of the MAC nucleophile enables the one-pot preparation of α-quaternary carboxylic acids, esters, and amides with a high degree of enantioselectivity. Finally, the first enantioselective transition metal-catalyzed allylic alkylation providing access to acyclic products bearing vicinal all-carbon quaternary centers is presented.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Iridium, allylic alkylation, catalytic, stereoselective
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)
  • Grubbs, Robert H.
  • Dervan, Peter B.
  • Stoltz, Brian M.
Defense Date:25 May 2018
Funders:
Funding AgencyGrant Number
NIHF31 GM120804
Record Number:CaltechTHESIS:05302018-124410879
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:05302018-124410879
DOI:10.7907/S93J-6P85
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscatal.6b01886DOIReview article adapted for Prologue and Chapter 1
https://doi.org/10.1002/anie.201609960 DOICommunication adapted for Chapter 1
https://doi.org/10.1021/acs.orglett.7b00449DOICommunication adapted for Chapter 2
https://doi.org/10.1002/anie.201707015DOICommunication adapted for Chapter 3
https://doi.org/10.1002/anie.201804820DOICommunication adapted for Chapter 4
https://doi.org/10.1021/ol5031537DOICommunication adapted for Appendix 8
https://doi.org/10.1021/acs.oprd.5b00169DOIReview article adapted for Appendix 8
https://doi.org/10.1016/j.tetlet.2017.07.022DOICommunication adapted for Appendix 11
ORCID:
AuthorORCID
Shockley, Samantha Elizabeth0000-0001-5682-8569
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10974
Collection:CaltechTHESIS
Deposited By: Samantha Shockley
Deposited On:01 Jun 2018 18:27
Last Modified:04 Oct 2019 00:21

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