dc.contributor.advisor | Harmata, Michael, 1959- | eng |
dc.contributor.author | Hampton, Carissa Sue | eng |
dc.date.issued | 2014 | eng |
dc.date.submitted | 2014 Fall | eng |
dc.description.abstract | [ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] The [2,3]-sigmatropic rearrangement of propargylic sulfinates to allenic sulfones was studied under both silver and copper catalysis. Metal salts having non-coordinating anions were effective at promoting the rearrangement. In addition, recoverable and reusable metal-doped ultrastable Y (USY) zeolites are able to catalyze the rearrangement, making the process more environmentally "green". In the course of studying some organometallic chemistry of allenic sulfones, we discovered a facile palladium-catalyzed isomerization of these species to 1-arylsulfonyl 1,3-dienes. In the absence of palladium, but in the presence of a nucleophile and proton shuttle, such allenes can be converted to 2-arylsulfonyl 1,3-dienes. The mechanisms of both processes are examined. Troger?s base is a non-natural chiral amine whose analogues have applications in many areas. The sterics of Troger?s base prevent it from functioning as a bidentate ligand. We have designed a ligand derived from the Troger?s base structural framework that is dianionic and contains multiple coordination sites for transition metal and actinide complexation. | eng |
dc.identifier.uri | https://hdl.handle.net/10355/48210 | |
dc.identifier.uri | https://doi.org/10.32469/10355/48210 | eng |
dc.language | English | eng |
dc.publisher | University of Missouri--Columbia | eng |
dc.relation.ispartofcommunity | University of Missouri--Columbia. Graduate School. Theses and Dissertations | eng |
dc.rights | Access is limited to the campus of the University of Missouri--Columbia. | eng |
dc.subject.FAST | Chemistry, Organic | eng |
dc.subject.FAST | Palladium | eng |
dc.subject.FAST | Sulfinic acids | eng |
dc.title | [2,3]-Sigmatropic rearrangement of propargylic sulfinates ; Regiodivergent synthesis of 1- and 2 arylsulfonyl 1,3-dienes, and III. Synthesis of Troger's base-derived ligands | eng |
dc.type | Thesis | eng |
thesis.degree.discipline | Chemistry (MU) | eng |
thesis.degree.grantor | University of Missouri--Columbia | eng |
thesis.degree.level | Doctoral | eng |
thesis.degree.name | Ph. D. | eng |