Transition metal induced vicinal difunctionalization of olefins: Aminohalogenation and diamination for the rapid assembly of nitrogen heterocycles
Zabawa, Thomas Paul
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Chapter 1- Palladium(II) Catalyzed Aminohalogenation of Olefins. Vicinal haloamines are versatile building blocks for organic synthesis and the vicinal 1,2-haloarnine moiety is also prevalent in biologically active molecules. A direct intramolecular aminohalogenation reaction is synthetically attractive due to the atom- economical simultaneous formation of both a heterocycle, and a halogenated carbon, which can act as a synthetic handle for further elaboration. Herein is reported the first palladium(II) catalyzed intramolecular aminobromination and chlorination of unactivated olefins. The aminohalogenation reaction is promoted by stoichiometric amounts of copper(II) halide salt additives. Reaction optimization was examined by examining the nature of the copper(II) salt, solvent and temperature effects. High yields resulted for a number of structurally different substrates. Chapter 2- Cu(II) Carboxylate Promoted Intramolecular Diamination of Unactivated Olefins. The 1,2-diamine moiety is considered a privileged structural functionality in biologically active compounds. A wide range of medicinal agents contain the vicinal diamine unit. Diamines are also useful synthetic agents serving as both chiral auxiliaries and ligands for transition metal catalysis. Herein is reported a copper(II) carboxylate promoted intramolecular diamination of unactivated olefins. High yields are reported for a variety of structurally diverse diamine substrates. The formation of both five- and six- membered sulfamide heterocycles, as well as cyclic ureas bis(anilines), and ∝-amido pyrroles was accomplished. High substrate based diastereoselectivity was also observed in the synthesis of 2,5-disubstituted pyrrolidines.