Stereoselective Syntheses of Nitrogen Heterocycles via Copper(II)-Promoted and Catalyzed Aminooxygenation of Alkenes
Paderes, Monissa Cuebillas
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In this dissertation, the development of the copper(II)-promoted and catalyzed intramolecular aminooxygenation reaction of unactivated alkenes is discussed. This method provides an efficient strategy to access nitrogen heterocycles in stereoselective manner. This thesis is divided into four Chapters. Chapter One describes the advances in intra- and intermolecular aminooxygenation reaction of olefins catalyzed and promoted by various other transition metals. Our developed copper(II)-promoted diastereoselective protocol and its application to the formal synthesis of (+)-monomorine is also presented. In Chapter Two, the successful development of a high-yielding copper(II)-catalyzed diastereoselective alkene aminooxygenation method that uses O 2 (1 atm) as the stoichiometric oxidant is discussed. The enantioselectivity and diastereoselectivity of the reaction was further improved with choice of copper(II) catalyst and substrate's N -substituent. In Chapter Three, a combined detailed experimental and theoretical mechanistic study on the copper(II)-promoted alkene aminooxygenation is discussed. Rigorous evidence on the proposed mechanism was provided. A subsequent detailed mechanistic study on the catalytic enantioselective reaction is presented in Chapter Four. An improved reaction conditions, enantioselectivity and a scale-up reaction were also described.