摘要
目前,手性配体辅助钯催化的区域和对映选择性碳氢键活化是过渡金属催化的前沿领域.在过去的十年中,它作为一种越来越重要的合成工具,用于合成含有各种不对称元素(中心手性、轴手性和平面手性)的手性分子,也是快速构建各种碳碳键和碳杂原子键的最有效方法之一.本文介绍了一些典型手性配体在钯催化不对称sp^(2)和sp^(3)碳氢键活化/官能团化反应中的应用,如单齿配体亚磷酰胺、手性磷酸(CPAs)和双功能氮端单保护的氨基酸(MPAAs)配体;探讨了这些手性配体辅助催化反应的创新性和特点,在理清这一研究领域发展脉络的同时,展望了未来研究工作的方向.此外,本文还介绍了这一不对称合成策略在天然产物、药物分子全合成中的应用.
Chiral ligands enabled palladium-catalyzed regio-and enantioselective C–H activation represents one of the current frontiers in transition metal catalysis. It has been extensively developed over the past decade as an important method for the synthesis of chiral molecules. Functional molecules bearing central, axial or planar chirality can be efficiently generated in good to excellent optical purities through this method. It has also been used as one of the most efficient methods for the rapid construction of various C–C and C–X bonds. In this review, we highlight the development of some representative chiral ligands in Pd-catalyzed enantioselective C(sp^(2))–H and C(sp^(3))–H functionalization reactions. Specifically, critical features of these novel Pd-catalyzed transformations assisted by chiral ligands such as monodentate phosphoramidites, chiral phosphoric acids(CPAs) and bifunctional mono-N-protected amino acids(MPAAs) will be discussed. The recent advances and limitations in this rapidly growing research area and its application in the total synthesis of natural products and pharmaceutical molecules will also be presented and discussed.
作者
杜宇
黄永亮
高越
沈慧
苏伟平
洪茂椿
Yu Du;Yongliang Huang;Yue Gao;Hui Shen;Weiping Su;Maochun Hong(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2021年第2期123-143,共21页
SCIENTIA SINICA Chimica
关键词
手性配体
碳氢键活化
钯催化
亚磷酰胺
手性磷酸
氮端单保护氨基酸
chiral ligand
carbon-hydrogen activation
palladium catalysis
phosphoramidite
chiral phosphoric acid
mono-N-protected amino acid
