使用N-杂环卡宾稳定的零价镍配合物进行化学计量和催化的芳基氯活化及硼化反应。
Stoichiometric and Catalytic Aryl-Cl Activation and Borylation using NHC-stabilized Nickel(0) Complexes.
作者信息
Kuehn Laura, Jammal Dominik G, Lubitz Katharina, Marder Todd B, Radius Udo
机构信息
Institut für Anorganische Chemie and Institute for Sustainable Chemistry and Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
出版信息
Chemistry. 2019 Jul 17;25(40):9514-9521. doi: 10.1002/chem.201900937. Epub 2019 Apr 11.
NHC-nickel (NHC=N-heterocyclic carbene) complexes are efficient catalysts for the C-Cl bond borylation of aryl chlorides using NaOAc as a base and B pin (pin=pinacolato) as the boron source. The catalysts [Ni (ICy) (μ-(η :η )-COD)] (1, ICy=1,3-dicyclohexylimidazolin-2-ylidene; COD=1,5-cyclooctadiene), [Ni(ICy) (η -C H )] (2), and [Ni(ICy) (η -COE)] (3, COE=cyclooctene) compare well with other nickel catalysts reported previously for aryl-chloride borylation with the advantage that no further ligands had to be added to the reaction. Borylation also proceeded with B neop (neop=neopentylglycolato) as the boron source. Stoichiometric oxidative addition of different aryl chlorides to complex 1 was highly selective affording trans-[Ni(ICy) (Cl)(Ar)] (Ar=4-(F C)C H , 11; 4-(MeO)C H , 12; C H , 13; 3,5-F C H , 14).
NHC-镍（NHC = N-杂环卡宾）配合物是以醋酸钠为碱、频哪醇硼酸酯（pin = 频哪醇硼酸酯）为硼源时，芳基氯化物C-Cl键硼化反应的高效催化剂。催化剂[Ni(ICy)(μ-(η:η)-COD)]（1，ICy = 1,3-二环己基咪唑啉-2-亚基；COD = 1,5-环辛二烯）、[Ni(ICy)(η-C₆H₆)]（2）和[Ni(ICy)(η-COE)]（3，COE = 环辛烯）与之前报道的用于芳基氯化物硼化反应的其他镍催化剂相比具有优势，即反应无需添加其他配体。以新戊二醇硼酸酯（neop = 新戊二醇硼酸酯）为硼源时也能进行硼化反应。不同芳基氯化物与配合物1的化学计量氧化加成反应具有高度选择性，生成反式-[Ni(ICy)(Cl)(Ar)]（Ar = 4-(F₃C)C₆H₄，11；4-(MeO)C₆H₄，12；C₆H₅，13；3,5-F₂C₆H₃，14）。
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