Application of Dewar Heterocycles and Vinyl Carbocations in Organic Synthesis

Citation

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. https://resolver.caltech.edu/CaltechTHESIS:06072023-204031343

Abstract

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.

Thesis Files