Copper-Catalyzed Synthesis of Alkyl Fluorides, Sterically Hindered Anilines, and 1,4-Dienes
Mailig, Melrose Tolosa
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Copper is a versatile transition metal and has been used as a catalyst for constructing a variety of bonds in organic synthesis. It is relatively abundant, cheap, and less toxic than other transition metals, making it an advantageous catalyst. Presented in this thesis are three new copper-catalyzed reactions for the preparation of alkyl fluorides, sterically hindered anilines, and 1,4-dienes. These classes of compounds can be found in nature and have important application in medicinal chemistry and the pharmaceutical industry. Finally, we have also demonstrated the utility of these reactions in the construction of useful organic compounds. Chapter 1 describes the copper-catalyzed fluorination of alkyl triflates for the synthesis of alkyl fluorides. This reaction uses a transition-metal complex as an efficient phase-transfer catalyst under mild reaction conditions. No elimination byproducts were observed when using the optimized reaction conditions. This addresses a long standing issue in alkyl fluoride synthesis. Chapter 2 describes the copper-catalyzed coupling of aryl boronic esters with O-benzoyl hydroxylamines for the synthesis of sterically hindered N,N-dialkyl anilines and N-alkyl anilines. This reaction uses an air stable and commercially available precatalyst and a mild turn over reagent, thus making this reaction a practical method to synthesize anilines. Chapter 3 describes the anti-Markovnikov hydroallylation of terminal alkynes and nonsymmetrical dialkyl substituted alkynes to provide a variety of 1,4-dienes and trisubstituted alkenes. The hydroallylation is syn-stereospecific and highly-regioselective allowing access to stereodefined trisubstituted olefins.
- Chemistry