The atom-economic conversion of chemical feedstocks into biologically relevant complex molecules in a stereocontrolled fashion remains a continuous challenge to synthetic chemists. In this context, the use of simple ambiphilic starting materials as linchpins allows a bidirectional increase of molecular complexity from widely available precursors. Here, we report the use of branched aldehydes as versatile linchpins for various Zn-ProPhenol-catalysed C–C bond-forming reactions to efficiently construct enantioenriched 1,3-aminoalcohols bearing an acyclic quaternary stereogenic centre. The ability of the Zn-ProPhenol catalyst to selectively activate ambiphilic aldehydes first as nucleophiles for Mannich reactions and then as electrophiles for aldol, Henry and alkyne addition reactions allows for the one-pot synthesis of complex stereotriads from common building blocks. Moreover, this approach can be diastereodivergent by simply selecting the proper catalyst combination. Overall, this catalytic method directly transforms simple and readily available aldehydes into highly functionalized compounds and provides streamlined access to valuable 1,3-aminoalcohols relevant to the synthesis of biologically important molecules.

化学原料的原子经济转化为生物相关的复杂分子以立体控制方式仍然是合成化学家的持续挑战。在这种情况下，使用简单的双生起始原料作为关键，可以从广泛使用的前体中双向增加分子的复杂性。在这里，我们报告了支化醛作为各种Znpin-酚催化的C–C键形成反应的通用缩钉的作用，以有效地构建对映体富集的1，3-氨基醇，并带有一个无环季铵立体中心。Zn-ProPhenol催化剂选择性活化两性醛的能力，首先将其作为曼尼希反应的亲核试剂，然后再将其作为醛醇的亲电试剂，亨利（Henry）和炔烃（alkyne）加成反应可从常见的结构单元一锅合成复杂的立体三单元组。而且，通过简单地选择合适的催化剂组合，该方法可以是非对映的。总体而言，这种催化方法将简单易用的醛直接转化为高度官能化的化合物，并简化了对与生物重要分子的合成有关的有价值的1,3-氨基醇的获取。