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Development of Enantioselective Transition-Metal Catalyzed Allylic Alkylation Methodologies

Citation

Alexy, Eric John (2020) Development of Enantioselective Transition-Metal Catalyzed Allylic Alkylation Methodologies. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/41nh-wb31. https://resolver.caltech.edu/CaltechTHESIS:05222020-215559562

Abstract

Research in the Stoltz group is directed, generally, at the development of synthetic methods for the preparation of stereochemically rich molecules, and the total synthesis of complex natural products. One major theme of our group’s methods development is transition-metal catalyzed allylic alkylation, of which we have reported Pd, Ir, Cu, and Ni catalyzed strategies. Described in this thesis are projects related to these interests, primarily focused on new approaches toward acyclic stereocenters via palladium catalysis; however also include an iridium-catalyzed formal γ-alkylation of malonates and β-ketoesters, as well as an Overman rearrangement strategy for synthesizing α-amino ketones. A majority of asymmetric enolate functionalization methods, developed by our group and others, pertain to cyclic systems in which only one enolate geometry isomer is possible due to the constrained ring. In acyclic systems, however, this issue of enolate geometry becomes a major challenge that must be addressed. When one seeks to prepare a tetrasubstituted acyclic enolate, which would lead to a fully-substituted stereocenter following functionalization, one must contend with the issue of non-selective formation of a mixture of enolates which generally leads toward less selective transformations. Strategies toward overcoming this issue, as well as new insights gained regarding the palladium-catalyzed alkylation of acyclic enolates, are described in the subsequent chapters.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Transition-metal catalysis, allylic alkylation, palladium-catalysis, enantioselective catalysis
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)
  • Blake, Geoffrey A.
  • Robb, Maxwell J.
  • Stoltz, Brian M.
Defense Date:19 May 2020
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipUNSPECIFIED
NIHR01GM080269-01
Record Number:CaltechTHESIS:05222020-215559562
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:05222020-215559562
DOI:10.7907/41nh-wb31
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.6b02153DOIArticle adapted for Chapter 1.
https://doi.org/10.1021/acs.orglett.7b02354DOIArticle adapted for Chapter 2.
https://doi.org/10.1021/jacs.8b05560DOIArticle adapted for Chapter 3.
https://doi.org/10.1039/C9SC01726GDOIArticle adapted for Chapter 4.
https://doi.org/10.1002/adsc.201901281DOIArticle adapted for Chapter 5.
https://doi.org/10.1021/acs.orglett.0c01303DOIArticle adapted for Chapter 6.
ORCID:
AuthorORCID
Alexy, Eric John0000-0002-2971-9698
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13716
Collection:CaltechTHESIS
Deposited By: Eric Alexy
Deposited On:01 Jun 2020 22:06
Last Modified:27 Oct 2021 23:43

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