The syntheses of (+)-zincophorin methyl ester and graphene nanomaterials through redox-triggered coupling
dc.contributor.advisor | Krische, Michael J. | |
dc.contributor.committeeMember | Rose, Michael | |
dc.contributor.committeeMember | Anslyn, Eric V | |
dc.contributor.committeeMember | Keatinge-Clay, Adrian T | |
dc.contributor.committeeMember | Martin, Stephen F | |
dc.creator | Kasun, Zachary Alexander | |
dc.date.accessioned | 2018-10-04T15:28:36Z | |
dc.date.available | 2018-10-04T15:28:36Z | |
dc.date.created | 2018-08 | |
dc.date.issued | 2018-07-31 | |
dc.date.submitted | August 2018 | |
dc.date.updated | 2018-10-04T15:28:36Z | |
dc.description.abstract | (+)-Zincophorin methyl ester was prepared in 13 steps (LLS) representing a concise route to this iconic natural product. A bidirectional redox-triggered double anti-crotylation of 2-methyl-1,3-propane diol directly assembles the triketide stereopolyad spanning C4−C12, significantly enhancing step economy and enabling construction of (+)-zincophorin methyl ester in nearly half the steps previously required. A method for the ring expansion of cyclic diols is described. Using improved conditions for the ruthenium(0) catalyzed cycloaddition of cyclic 1,2-diols with 1,3-dienes, fused [n.4.0] bicycles (n = 3-6) are formed, which upon exposure to (diacetoxyiodo)benezene engage in oxidative cleavage to form 9–12 membered rings. Alternating ortho, para-oligophenylenes were prepared employing ruthenium catalyzed cycloaddition. Poly-ols prepared through dihydroxylation of vinyl-phenylene oligomers were subjected to benzannulation through ruthenium(0) catalyzed cycloaddition with butadiene followed by acid-catalyzed double dehydration. Further dehydrogenation under Scholl oxidation conditions furnished nanographene materials. This approach employs relatively inexpensive ruthenium catalysts, and stoichiometric organometallic reagents are not required. This benzannulation of tris-thiophene containing 1,2-diols were also subject to benzannulation to prepare triopodal oligophenylenes terminated with thiophenes. Dimerizaiton of these united via lithiation and cuprate formation provided helical dimerized product. | |
dc.description.department | Chemistry | |
dc.format.mimetype | application/pdf | |
dc.identifier | doi:10.15781/T2ZK56564 | |
dc.identifier.uri | http://hdl.handle.net/2152/68693 | |
dc.language.iso | en | |
dc.subject | Natural product synthesis | |
dc.subject | Nanographenes | |
dc.subject | Organic chemistry | |
dc.title | The syntheses of (+)-zincophorin methyl ester and graphene nanomaterials through redox-triggered coupling | |
dc.type | Thesis | |
dc.type.material | text | |
thesis.degree.department | Chemistry | |
thesis.degree.discipline | Chemistry | |
thesis.degree.grantor | The University of Texas at Austin | |
thesis.degree.level | Doctoral | |
thesis.degree.name | Doctor of Philosophy |
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