Amines are the most pivotal class of organic motifs in pharmaceutical compounds. Here we provide a blueprint for a general synthesis of amines by catalyst differentiation enabled by triple Au–H/Au⁺/Au–H relay catalysis. The parent catalyst is differentiated into a set of catalytically active species to enable triple cascade catalysis, where each catalytic species is specifically tuned for one catalytic cycle. This strategy enables the synthesis of biorelevant amine motifs by reductive hydroamination of alkynes with nitroarenes. Using this triple cascade approach, we have achieved exceptional functional group tolerance, enabling the use of bulk chemical feedstocks as coupling partners for the amination of both simple and complex alkynes (>100 examples), including those derived from pharmaceuticals, peptides and natural products (>30 examples). The isolation and full crystallographic characterization of gold hydride and hydride-bridged gold complexes has garnered insights into the catalyst differentiation process of fundamental organometallic gold hydride complexes.

胺是药物化合物中最关键的一类有机基序。在这里，我们提供了通过三重 Au-H/Au⁺/Au-H 中继催化实现的催化剂分化一般合成胺的蓝图。母体催化剂被分化为一组催化活性物质，以实现三级联催化，其中每个催化物质都针对一个催化循环进行了专门调整。该策略能够通过炔烃与硝基芳烃的还原性氢胺化合成生物相关胺基序。使用这种三重级联方法，我们实现了卓越的官能团耐受性，能够使用大宗化学原料作为简单和复杂炔烃（>100例子）的胺化偶联伙伴，包括来自药物、肽和天然产物的炔烃（>30例子）。氢化金和氢化物桥式金配合物的分离和全晶体学表征为基本有机金属金氢化物配合物的催化剂分化过程提供了见解。