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Selective Carbon-Carbon Bond Formation Promoted By Divalent Samarium Reagents, Christopher David-James Aretz

Electronic Theses and Dissertations

Three efficient methods for synthesis of five membered carbocycles, a highly understudied product motif in samarium(II) chemistry, were explored and optimized. These methods utilized simple starting materials to generate linear substrates with functional groups that are reactive towards samarium(II) iodide. The three methods explored were the Reformatsky-aldol, Reformatsky-alkylation, and pinacol cyclizations. The critical discovery for efficient formation of the Reformatsky-aldol and pinacol carbocycles products was the use of lithium bromide. This addition of lithium bromide facilitates easy in situ formation of samarium(II) bromide. The Reformatsky-alkylation cyclization was a newly realized reaction employing samarium enolates. Two of the three methods, the …

Brønsted Acid Catalyzed Carbon-Carbon Bond Forming Reactions, Jiangyue Miao

Electronic Theses and Dissertations

The focus of this research project lies in the development of new methodology in the field of Brønsted acid catalysis enabling rapid synthesis of medicinally relevant compounds. It is foreseen that small molecule sulfonic acids evaluated in this research project will unveil new asymmetric carbon carbon bond forming reactions between substrates hitherto unexplored with Brønsted acid catalysis. It has been established that strong Brønsted acids, such as phosphoric acids, are capable of mediating highly selective transformations operating through unique mechanistic manifolds.

Specific focus for the sulfonic acid catalysts was geared towards asymmetric coupling reactions with synthetically useful precursors such as …