Ciufolini, Marco A.2009-06-042009-06-041991Byrne, Norman Edward. "New approaches to total synthesis of quinoid antitumor agents: Cystodytins and discorhabdins." (1991) Diss., Rice University. <a href="https://hdl.handle.net/1911/16424">https://hdl.handle.net/1911/16424</a>.https://hdl.handle.net/1911/16424A new pyridine synthesis is described. The key step involves a modified Knoevenagel-Stobbe reaction in which the treatment of an alkoxy-dihydropyran with hydroxylamine hydrochloride generates highly substituted pyridine ring systems. Approaches to efficient syntheses of important natural products in including aza-analogs of polynuclear aromatic hydrocarbons, Eupolauramine, and Streptonigrin are explored. Antitumor agents Cystodytin A and B were synthesized in 13 steps from 4-hydroxyethyl cyclohexanone in an overall yield of 7%. This efficient total synthesis involves the new pyridine reaction and a photochemical nitrene insertion as crucial steps. Various approaches are explored toward the total synthesis of antitumor agent Discorhabdin C. The first synthetically useful Paterno-Buchi reaction between benzoquinone and an olefin was discovered. Various applications of this reaction are described, including its use for the synthesis of Discorhabdin C.449 p.application/pdfengCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.Organic chemistryThesisThesis Chem. 1991 Byrne