Title

NEW CARBON-CARBON BOND-FORMING REACTIONS OF ENDOCYCLIC AND EXOCYCLIC ENOL ETHERS

Date of Award

December 2017

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor(s)

Nancy I. Totah

Second Advisor

Robert B. Silver

Subject Categories

Physical Sciences and Mathematics

Abstract

Abstract of the Dissertation

Metal-catalyzed Alder-ene reactions have been utilized for atom efficient carbon-carbon bond-forming reactions. Ruthenium-catalyzed Alder-ene reactions are examined here, specifically the chemistry of exocyclic enol ethers, and their reactivity with simple alkynes to generate 1,4-dienes. Ruthenium-catalyzed Alder-ene reactions are mild, a consideration when using exocyclic enol ethers due to their acid-and-water sensitive nature.

Here, 2-methylenetetrahydropyrans were used to form new carbon-carbon bonds with alkynes in an Alder ene-type manner. When forming new carbon-carbon bonds, the ruthenium catalyst CpRu(MeCN)3PF6 was found to tolerate a number of different functional groups on the alkynes including electronically and sterically different substituents.

Trichloroacetimidates can be mild alkylating agents under acidic conditions as the alkylation is driven by the formation of trichloroacetamide , or amide. This process provides a substantial thermodynamic driving force due to the newly formed-double bonded carbon and (or carbonyl) oxygen. In the presence of an acid, catalyst trichloroacetimidates can react with unsaturated systems to form new carbon-carbon bonds. In this, new carbon-carbon bond formation can be used to gain access a spectrum of new organic compound syntheses.

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