Jiang Tianxiao, Zhang Haocheng, Ding Yongzheng, Zou Suchen, Chang Rui, Huang Hanmin
Hefei National Laboratory for Physical Sciences at the Microscale, and Department of Chemistry, Center for Excellence in Molecular Synthesis, University of Science and Technology of China, Chinese Academy of Sciences, Hefei, 230026, P. R. China.
Chem Soc Rev. 2020 Mar 7;49(5):1487-1516. doi: 10.1039/c9cs00539k. Epub 2020 Jan 30.
Reductive elimination is a crucial bond-forming elementary reaction in various transition-metal mediated reactions. Apart from the well-developed classic reductive elimination, the non-classic reductive elimination occurring between a covalent ligand and a dative ligand, which has been known for over 50 years, has gradually attracted much attention from the organic community. By avoiding pπ-dπ repulsion between the filled metal d-orbital and the filled ligand p-orbital and forming a cationic-type molecule, non-classic reductive elimination could facilitate many catalytic reactions that were difficult to be realized via classic reductive elimination. In this review, transition-metal catalyzed C-P, C-S, C-N, and C-C bond-forming reactions with non-classic reductive elimination as the key elementary step are summarized.
还原消除是各种过渡金属介导反应中至关重要的成键基元反应。除了已充分发展的经典还原消除反应外，共价配体与给予体配体之间发生的非经典还原消除反应，虽已被知晓五十多年，但逐渐引起了有机化学界的广泛关注。通过避免填充金属d轨道与填充配体p轨道之间的pπ-dπ排斥并形成阳离子型分子，非经典还原消除能够促进许多难以通过经典还原消除实现的催化反应。在本综述中，总结了以非经典还原消除为关键基元步骤的过渡金属催化的C-P、C-S、C-N和C-C成键反应。
