Chiral aliphatic amines are privileged functionalities in pharmaceutical molecules and play an essential role as ligands and catalysts in organic synthesis. It is therefore important to develop efficient catalytic strategies to access aliphatic amines in an enantiopure form. Despite great advancement in asymmetric amination methods, including reductive amination and C–N cross coupling, direct access to diverse enantioenriched aliphatic amines from readily available feedstocks is still lacking. Herein, we demonstrate direct enantioconvergent amination of racemic secondary alcohols using a variety of aliphatic primary amines, under the cooperative catalysis of a chiral iridium complex with a chiral phosphoric acid. This strategy realizes a challenging catalytic redox-neutral cascade without the need for any stoichiometric reagent, offering a one-step conversion of feedstock substrates to valuable chiral aliphatic secondary amines in high yield and enantioselectivity. The use of this atom-economical carbon–nitrogen bond-forming strategy is illustrated by the enantioselective synthesis of commercial drugs and their analogues. Futhermore, we discovered an intriguing racemization pathway for chiral aliphatic amines, which delivers important guiding principles for redox-related stereoselective control in chiral amine synthesis.

手性脂肪胺是药物分子中的特殊功能，在有机合成中作为配体和催化剂发挥着重要作用。因此，重要的是开发有效的催化策略以获取对映体纯形式的脂肪胺。尽管不对称胺化方法取得了很大进步，包括还原胺化和 C-N 交叉偶联，但仍然缺乏从现成原料中直接获取多种对映体富集脂肪胺的方法。在此，我们展示了在手性铱络合物与手性磷酸的协同催化下，使用多种脂肪族伯胺对外消旋仲醇进行直接对映收敛胺化。该策略实现了具有挑战性的催化氧化还原中性级联，而不需要任何化学计量试剂，以高产率和对映选择性将原料底物一步转化为有价值的手性脂肪族仲胺。商业药物及其类似物的对映选择性合成说明了这种原子经济碳氮键形成策略的使用。此外，我们发现了一种有趣的手性脂肪胺外消旋化途径，它为手性胺合成中氧化还原相关的立体选择性控制提供了重要的指导原则。