Term | Value | Language |
---|---|---|
dc.contributor.advisor | Johnson, Darren | |
dc.contributor.author | Phan, Ngoc | |
dc.date.accessioned | 2020-12-08T15:44:01Z | |
dc.date.available | 2020-12-08T15:44:01Z | |
dc.date.issued | 2020-12-08 | |
dc.identifier.uri | https://scholarsbank.uoregon.edu/xmlui/handle/1794/25878 | |
dc.description.abstract | Self-assembly involves the self-driven incorporation of smaller components into large molecules, a process analogous to a puzzle programmed to put itself together. Nature has made use of self-assembly in biological processes such as the formation of double helical DNA. In chemical synthesis, the importance of disulfide bridges in proteins has spurred the development of processes that can direct thiols to self-assemble into disulfides. The DWJ laboratory has introduced the use of metalloids as an additive that enables the rapid and selective self-assembly of thiols into complex disulfide structures. We are able to trap these disulfides as the more stable thioethers in high yield, with the process taking under two days as compared to lengthy syntheses (several weeks) with traditional methods. This Dissertation describes an effort to improve our previously published method. The study on the role of the Group 15 elements (or pnictogens) in the self-assembly process has led to the discovery of copper(II) as an alternative directing group. While both the pnictogens and copper(II) are important reagents in the self-assembly reaction, the latter additive is a more environmentally benign option, and its directing ability has been demonstrated by the synthesis of 13 new disulfides and thioethers in two steps. Expanding the scope of our method, new unsymmetrical disulfides and thioethers have been made by mixing two different thiols. Instead of a statistical distribution of products, different-sized disulfides (dimers, trimers, tetramers) have been amplified through various reaction conditions. For instance, the yield of the unsymmetrical trimers could be amplified to 65% from the statistical yield of 20%. The ability to selectively prepare unsymmetrical disulfide and thioether species can have a significant impact on the current synthetic field, which is dominated by symmetrical, dimeric species constructed from traditional methods. Finally, photochemical sulfur extrusion has been applied on the thioether cyclophanes to give hydrocarbon cyclophanes. The four new hydrocarbon cyclophanes synthesized using our new method are very challenging to obtain with traditional methods. These new hydrocarbon structures will be great targets for fundamental studies and may lead to potential new monomers for insulating plastics in the $1B US polymerization market. | en_US |
dc.language.iso | en_US | |
dc.publisher | University of Oregon | |
dc.rights | All Rights Reserved. | |
dc.subject | covalent capture | en_US |
dc.subject | disulfide | en_US |
dc.subject | hydrocarbon | en_US |
dc.subject | photochemistry | en_US |
dc.subject | self-assembly | en_US |
dc.subject | thioether | en_US |
dc.title | Synthesis of Disulfide, Thioether, and Hydrocarbon Cyclophanes Using Self-Assembly, Covalent Capture, and Photochemical Sulfur Extrusion | |
dc.type | Electronic Thesis or Dissertation | |
thesis.degree.name | Ph.D. | |
thesis.degree.level | doctoral | |
thesis.degree.discipline | Department of Chemistry and Biochemistry | |
thesis.degree.grantor | University of Oregon |