Asymmetric Carbene Transformations for the Construction of All‐Carbon Quaternary Centers

Asymmetric catalytic carbene reactions have been well documented in the last few decades for the expeditious assembly of chiral molecules with structural diversity. However, the enantioselective construction of all‐carbon quaternary centers remains a challenge in this area. In this review article, two types of asymmetric carbene reactions that beyond cyclopropanation, cyclopropenation, and Büchner reaction, have been summarized for the construction of all‐carbon quaternary centers: 1) using carbene species as a 1C synthon that reacts with a trisubstituted prochiral center; 2) sequential installation of two different C−C bonds on the carbene position, which features a gem‐difunctionalization reaction. Especially, the asymmetric metal carbene gem‐dialkylation process, which has emerged as a practical and versatile method for the expeditious assembly of complex architectures from readily available chemical resources, is a complementary approach for the expeditious assembly of all‐carbon quaternary centers. Two types of asymmetric carbene reactions for the construction of all‐carbon quaternary center have been summarized: 1) using carbene species as a 1C synthon that reacts with a trisubstituted prochiral center; 2) sequential installation of two different C−C bonds on the carbene position, which features a gem‐difunctionalization process.