Ye Zhong-Tian, Wu Zhong-Wei, Zhang Xue-Xin, Zhou Jian, Yu Jin-Sheng
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. China.
Key Laboratory of Tropical Medicinal Resource Chemistry of Ministry of Education, Hainan Normal University, Haikou 571158, P. R. China.
Chem Soc Rev. 2024 Aug 27;53(17):8546-8562. doi: 10.1039/d4cs00417e.
Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal chemistry, and materials science. In this context, various asymmetric catalytic methods have been established for the diverse synthesis of silicon-stereogenic silanes. In particular, asymmetric organocatalysis is emerging as an important and complementary synthetic tool for the enantioselective construction of silicon-stereocenters, along with the rapid development of chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized silicon-stereogenic organosilanes with structural diversity, and should lead to great development in chiral organosilicon chemistry. In this Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations of prochiral tetraorganosilanes and dynamic kinetic asymmetric transformations of racemic organosilanes by employing five organocatalytic activation modes. The advantages, limitations and synthetic value of each protocol, as well as the synthetic opportunities still open for further exploration, are also discussed.
含硅手性中心的手性有机硅烷在合成化学、药物化学和材料科学领域的应用日益广泛。在此背景下，已开发出多种不对称催化方法用于多样合成含硅手性中心的硅烷。特别是，随着手性金属催化方法的迅速发展，不对称有机催化作为对映选择性构建硅手性中心的一种重要且互补的合成工具正在兴起。它的出现为实现具有结构多样性的功能化含硅手性中心的有机硅烷提供了一个强大的平台，并将引领手性有机硅化学的巨大发展。在本教程综述中，我们从两个方面突出这些最新成果：前手性四有机硅烷的去对称化以及通过采用五种有机催化活化模式实现外消旋有机硅烷的动态动力学不对称转化。还讨论了每种方法的优点、局限性和合成价值，以及仍有待进一步探索的合成机会。
