Copper-catalyzed functionalization of alkenes: Carboamination, C-H amination, C-H alkylation and carboetherifcation reactions
Liwosz, Timothy Walter
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Synthetic organic chemistry is a tool used to transform relatively simple starting materials to something much more complex. The functionalization of alkenes is a method that enables the construction of more complex structures, notably nitrogen and oxygen heterocycles, enamines and alkylated alkenes. The research presented herein examines a number of new reactions for the funtionalization of alkenes. In chapter I, we report a copper-catalyzed enantioselective intra/intermolecular carboamination of alkenes. The method cyclizes a number γ-alkenylsulfonamides and a δ-alkenylsulfonamide in the presence of a range of vinyl arenes and results in variously functionalized 2-substituted chiral nitrogen heterocycles via a formal alkene C-H functionalization process. Chapter II is focused on the copper-catalyzed oxidative C-H amination of alkenes. Reactions between N-aryl sulfonamides and vinyl arenes furnish enamides, allylic amines, indoles, benzothiazine dioxides, and dibenzazepines directly and efficiently. Control experiments further showed that MnO 2 alone can promote the reaction in the absence of a copper salt, albeit with lower efficiency. Chapter III is focused on the copper-catalyzed oxidative heck reactions between alkyltrifluoroborates and vinyl arenes. We present the studies that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. In addition to the alkyl Heck reaction, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Chapter IV is my contributions to the copper-catalyzed enantioselective carboetherification of alkenes. Chiral saturated oxygen heterocycles are important components of bioactive compounds. We reported a highly efficient enantioselective copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans.