Manganese‐Catalyzed Asymmetric Formal Hydroamination of Allylic Alcohols: A Remarkable Macrocyclic Ligand Effect

Abstract A unique family of chiral peraza N 6 ‐macrocyclic ligands, which are conformationally rigid and have a tunable saddle‐shaped cavity, is described. Utilizing their manganese(I) complexes, the first example earth‐abundant transition metal‐catalyzed asymmetric formal anti‐Markovnikov hydroamination allylic alcohols was realized, providing practical access to synthetically important γ‐amino in excellent yields enantioselectivities (up 99 % yield 98 ee). The single‐crystal structure Mn I complex indicates that manganese atom coordinates with dialkylamine moiety bidentate fashion. Further DFT calculations revealed five six nitrogen atoms ligand were engaged multiple noncovalent interactions Mn, an isopropanol molecule, β‐amino ketone intermediate via coordination, hydrogen bonding, and/or CH⋅⋅⋅π state, showing remarkable role macrocyclic framework.