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Application of Dewar Heterocycles and Vinyl Carbocations in Organic Synthesis


Nistanaki, Sepand K. (2023) Application of Dewar Heterocycles and Vinyl Carbocations in Organic Synthesis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/m1t7-tm48.


High-energy molecules are frequently employed in the construction of organic molecules and materials in both academic and industrial settings. This thesis describes the application of two distinct classes of reactive molecules in organic synthesis: (1) Dewar heterocycles, which contain a highly strained bicyclic structure; (2) vinyl cations, a class of dicoordinated carbocations containing an electron-deficient carbon center bound to only two atoms. A description of our experimental work relevant to this thesis commences with the exploration of Dewar pyrone in the total synthesis of (±)-vibralactone. Next, the application of Dewar heterocycles to the synthesis of new strained-ring polymers will be discussed, including examples of post-polymerization strategies to access soluble poly(acetylene) derivatives and β-amino acid type polymers. Finally, the development of a catalytic asymmetric C–H insertion reaction of vinyl carbocations will be described, with an emphasis on reaction development, scope, and mechanism.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Total synthesis, polymer synthesis, 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)
  • Fu, Gregory C.
  • Peters, Jonas C.
  • Nelson, Hosea M.
Defense Date:5 June 2023
Funding AgencyGrant Number
USPHS National Research Service AwardT32GM008496
Record Number:CaltechTHESIS:06072023-204031343
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 2 adapted for Chapter 3 adapted for Chapter 4
Nistanaki, Sepand K.0000-0002-5252-803X
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16092
Deposited By: Sepand Nistanaki
Deposited On:08 Jun 2023 15:09
Last Modified:08 Nov 2023 00:48

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