Synthesis, reactivity and polymerization of bridged bicyclic twisted amides
Author(s)
Xu, Mizhi
Advisor(s)
Editor(s)
Collections
Supplementary to:
Permanent Link
Abstract
Amides are generally robust and hydrolytically resistant due to the nN-to-π*C=O conjugation. Twisted amides represent an unusual subclass of amides containing distorted, non-planar amide bonds as a consequence of geometric, steric or electronic effects. The most common approach to twisting the amide bond involves geometric constraint in the bridged bicyclic amide structure. Due to the disrupted amide resonance, twisted amides feature distinct reactivities compared to normal amides, including enhanced N-nucleophilicity, carbonyl-electrophilicity and “amino-ketone” reactivity. Despite the unusual structure and unique reactivity of twisted amides, their potential as monomers in polymerization has rarely been explored. In this dissertation, the polymerization of a [3.3.1] bicyclic twisted amide system is described through the halide-rebound (Chapter 2) and ring-opening metathesis strategies (Chapter 4). In addition, the remote substituent effects on modulating the geometry and reactivity of this twisted amide framework are investigated via computational and kinetic studies (Chapter 3). Finally, a new halide-abstraction strategy is disclosed in the synthesis of a highly strained [3.2.1] bicyclic twisted amide (Chapter 5).
Sponsor
Date
2021-12-08
Extent
Resource Type
Text
Resource Subtype
Dissertation