Vicinal difunctionalization of olefins: Aminohalogenation and carboamination for the rapid assembly of nitrogen heterocycles
Manzoni, Maria Rita
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Vicinal haloamines are versatile synthetic intermediates in organic synthesis as well as key subunits of enzymatic inhibitors. Thus, the achievement of a highly enantio-, regio-, and stereoselective aminohalogenation of olefins is an important challenge to the synthetic organic community. We discovered Pd(II)-catalyzed intramolecular aminohalogenation of olefins. This new method is facilitated by copper(II) halide salts, serving as both the halogen source and stoichiometric oxidant. Control experiments designed to detect the presence of uncatalyzed background were also performed. The effects of the halogen source, solvent, temperature, reaction time, catalyst, and substrate structure on the product distribution have been examined. Comparison of the product distribution under the respective reaction conditions provides insight into the mechanism of the aminohalogenation reaction. We explored conditions to improve of the regioselectivity of aminohalogenation and screened ligands for the development of an asymmetric variant.