Molybdenum Complex-Catalyzed <i>N</i>‑Alkylation\nof Bulky Primary and Secondary Amines

Aliphatic allylic amines are present in a large number\nof complex\nand pharmaceutically relevant molecules. The direct amination of allylic\nelectrophiles serves as the most common method toward the preparation\nof these motifs. However, the use of feedstock reaction components\n(allyl alcohol and aliphatic amine) in these transformations remains\na great challenge. Such a challenge primarily stems from the high\nLewis basicity and large steric hindrance of aliphatic amines, in\naddition to the low reactivity of allylic alcohols. Herein, we report\na general solution to these challenges. The developed protocol allows\nan efficient allylic amination of allyl alcohols with sterically bulky\naliphatic amines in the presence of an inexpensive earth-abundant\nmolybdenum complex. This simple and economic protocol also enables\nregioselective branched amination; the practicality of the reaction\nwas shown in an efficient, scaled-up synthesis of several drugs.