Structurally Diverse Bench‐Stable Nickel(0) Pre‐Catalysts: A Practical Toolkit for In Situ Ligation Protocols**
Structurally Diverse Bench‐Stable Nickel(0) Pre‐Catalysts: A Practical Toolkit for In Situ Ligation Protocols**
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结构多样化的基准 - 稳定镍 (0) 预催化剂：原位连接方案的实用工具包**
DOI：
10.1002/anie.202211794
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Gembicky, Milan
中科院分区：
文献类型：
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作者：
Tran, Van T.;Kim, Nana;Rubel, Camille Z.;Wu, Xiangyu;Kang, Taeho;Jankins, Tanner C.;Li, Zi‐Qi;Joannou, Matthew V.;Ayers, Sloan;Gembicky, Milan
最近的一系列研究集中在有机合成中利用镍催化的力量。这些努力得到了同时开发的具有不同结构和反应性的明确镍（预）催化剂的支持。在本报告中，我们提出了十种不同的实验室稳定、18电子、形式上零价的镍-烯烃配合物，它们是各种反应中有效的预催化剂。我们的研究包括制备新型、实验室稳定的 Ni(COD)(L) 配合物（COD=1,5-环辛二烯），其中 L=醌、环戊二烯酮、噻吩-S-氧化物和富烯。通过核磁共振、红外、单晶 X 射线衍射、循环伏安法、热重分析和自然键轨道分析进行表征，揭示了这些配合物的结构、键合和性质。在各种镍催化反应中的应用强调了该工具包中不同预催化剂的互补性。
A flurry of recent research has centered on harnessing the power of nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous development of well‐defined nickel (pre)catalysts with diverse structure and reactivity. In this report, we present ten different bench‐stable, 18‐electron, formally zero‐valent nickel–olefin complexes that are competent pre‐catalysts in various reactions. Our investigation includes preparations of novel, bench‐stable Ni(COD)(L) complexes (COD=1,5‐cyclooctadiene), in which L=quinone, cyclopentadienone, thiophene‐S‐oxide, and fulvene. Characterization by NMR, IR, single‐crystal X‐ray diffraction, cyclic voltammetry, thermogravimetric analysis, and natural bond orbital analysis sheds light on the structure, bonding, and properties of these complexes. Applications in an assortment of nickel‐catalyzed reactions underscore the complementary nature of the different pre‐catalysts within this toolkit.