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A unique family of chiral peraza N6‐macrocyclic ligands, which are conformationally rigid and have a tunable saddle‐shaped cavity, is described. Utilizing their manganese(I) complexes, the first example of earth‐abundant transition metal‐catalyzed asymmetric formal anti‐Markovnikov hydroamination of allylic alcohols was realized, providing a practical access to synthetically important chiral γ‐amino...
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