Regioselective hydroamination of unactivated alkenes via chelation-assisted nickel-hydride-catalysis

Abstract

The catalytic hydroamination is powerful technology for the direct installation of amino groups across alkenes, allowing the rapid construction of molecular complexity from readily available alkenes. Especially, hydroamination of unactivated alkenes remains challenging due to low reactivity and poor regioselectivity for two electronically and sterically similar carbons. Therefore, this dissertation describes three catalytic hydroamination reactions in regioselective manner using chelation-assisted nickel-hydride catalysis. In chapter 1, proximal-selective hdroamination of unactivated alkenes is demonstrated using strong coordination of bidentate directing group to synthesize unnatural amino acid derivatives. In chapter 2, γ-selective migratory hydroamination of unactivated alkenes is presented through the nickel catalyzed alkene isomerization by external phosphine ligand and the termination of isomerization by the formation of stable nickellacycle. In chapter 3, regio- and enantioselective hydroamination of unactivated alkenes bearing weakly coordinating amides or esters using commercially available chiral bisoxazoline (BOX) ligand is discussed.