Cobalt(III)-Catalyzed Enantioselective Intermolecular Carboamination by C−H Functionalization

High-valent cyclopentadienyl cobalt catalysis is a versatile tool for sustainable C−H bond functionalizations. To harness the full potential of this strategy, control of the stereoselectivity of these processes is necessary. Herein, we report highly enantioselective intermolecular carboaminations of alkenes through C−H activation of N-phenoxyamides catalyzed by CoIII-complexes equipped with chiral cyclopentadienyl (Cpx) ligands. The method converts widely available acrylates as well as bicyclic olefins into attractive enantioenriched isotyrosine derivatives as well as elaborated amino-substituted bicyclic scaffolds under very mild conditions. The outlined reactivity is unique to the CpxCoIII complexes and is complementary to the reactivity of 4d- and 5d- precious-metal catalysts.

高价环戊二烯基钴催化是可持续C-H键官能团化反应的一类通用工具。为充分发挥该策略的全部潜力，亟需对这类反应的立体选择性进行精准调控。在此，我们报道了一种由手性环戊二烯基（Cpx）配体修饰的三价钴（CoIII）配合物催化、通过N-苯氧基酰胺的C-H活化实现烯烃分子间碳胺化反应的高对映选择性合成方法。该方法可在极为温和的反应条件下，将易得的丙烯酸酯与双环烯烃分别转化为极具应用价值的对映富集型异酪氨酸衍生物，以及结构复杂的氨基取代双环骨架。所报道的该类反应仅为CpxCoIII配合物所独有，可作为4d、5d族贵金属催化剂反应体系的有力补充。