A novel concept for catalytic asymmetric coupling reactions is presented. Merging organocatalysis with single‐electron oxidation by using a catalytic amount of a copper(II) salt and air as the terminal oxidant, we have developed a highly stereoselective carbon–carbon oxidative coupling reaction of α,β‐unsaturated aldehydes. The concept relies on the generation of a dienamine intermediate, which is oxidized to an open‐shell activated species that undergoes highly selective γ‐homo‐ and γ‐heterocoupling reactions. In the majority of examples presented, only a single stereoisomer was formed.

中文翻译：

---

以空气为末端氧化剂的α，β-不饱和醛的催化不对称氧化γ偶联

提出了催化不对称偶联反应的新概念。通过使用催化量的铜（II）盐和空气作为末端氧化剂，将有机催化与单电子氧化相结合，我们开发了α，β-不饱和醛的高度立体选择性碳-碳氧化偶联反应。该概念依赖于二烯胺中间体的生成，该中间体被氧化成开壳活化的物种，该物种经历了高度选择性的γ均质和γ异质偶联反应。在给出的大多数实施例中，仅形成了一个立体异构体。