December 2023

Lewis base/transition-metal cooperatively catalyzed asymmetric transformations have attracted extensive attention as they offer complementary catalytic systems within the realm of cooperative catalysis. Recently, the synergistic use of Lewis bases in combination with earth-abundant 3d metals has emerged as a fascinating prospect, presenting an opportunity to move away from the reliance on noble metals and to explore novel catalytic processes. In this Account, we highlight our recent achievements regarding the chemistry and synthetic utility of isothiourea (ITU) activated C1-ammonium enolates and N-heterocyclic carbene (NHC)-bound homoenolate equivalents in conjunction with 3d transition-metal activated electrophiles. The remarkable success in the stereoselective construction of carbon–carbon and carbon–heteroatom bonds has led to significant contributions to stereodivergent synthesis.1 Introduction2 ITU/Copper Cooperative Catalysis3 NHC/Copper Cooperative Catalysis4 NHC/Nickel Cooperative Catalysis5 Conclusion