Yao Minghan, Dong Shanliang, Xu Xinfang
School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, 510006, China.
Chemistry. 2024 May 8;30(26):e202304299. doi: 10.1002/chem.202304299. Epub 2024 Mar 1.
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.
在过去几十年里，不对称催化卡宾反应已被充分记录，用于快速构建具有结构多样性的手性分子。然而，全碳季碳中心的对映选择性构建在该领域仍然是一个挑战。在这篇综述文章中，总结了两种用于构建全碳季碳中心的不对称卡宾反应，它们超越了环丙烷化、环丙烯化和布赫纳反应：1）使用卡宾物种作为与三取代前手性中心反应的1C合成子；2）在卡宾位置上顺序安装两个不同的C-C键，其特点是偕二官能化反应。特别是，不对称金属卡宾偕二烷基化过程已成为一种实用且通用的方法，可从易得的化学资源快速组装复杂结构，是快速组装全碳季碳中心的一种补充方法。
