Enantioconvergent reactions are pre-eminent in contemporary asymmetric synthesis as they convert both enantiomers of a racemic starting material into a single enantioenriched product, thus avoiding the maximum 50% yield associated with resolutions. All currently known enantioconvergent processes necessitate the loss or partial loss of the racemic substrate’s stereochemical information, thus limiting the potential substrate scope to molecules that contain labile stereogenic units. Here we present an alternative approach to enantioconvergent reactions that can proceed with full retention of the racemic substrate’s configuration. This uniquely stereo-economic approach is possible if the two enantiomers of a racemic starting material are joined together to form one enantiomer of a non-meso product. Experimental validation of this concept is presented using two distinct strategies: (1) a direct asymmetric coupling approach, and (2) a multicomponent approach, which exhibits statistical amplification of enantiopurity. Thus, the established dogma that enantioconvergent reactions require substrates that contain labile stereogenic units is shown to be incorrect.

对映体收敛反应在当代不对称合成中非常突出，因为它们将外消旋起始材料的两种对映体转化为单一对映体富集的产物，从而避免了与拆分相关的最大 50% 产率。所有目前已知的对映体聚合过程都需要外消旋底物的立体化学信息的损失或部分损失，从而将潜在的底物范围限制为含有不稳定立体异构单元的分子。在这里，我们提出了一种对映异构反应的替代方法，该方法可以在完全保留外消旋底物构型的情况下进行。如果外消旋起始材料的两种对映体连接在一起形成非内消旋产物的一种对映体，则这种独特的立体经济方法是可能的。使用两种不同的策略对该概念进行实验验证：（1）直接不对称偶联方法，以及（2）多组分方法，该方法表现出对映体纯度的统计放大。因此，对映体收敛反应需要含有不稳定立体异构单元的底物这一既定教条被证明是不正确的。