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In Situ Generation of ArCu from CuF2 Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient

机译:从CuF2原位生成ArCu使大体积芳基硅烷的偶联可行且高效

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摘要

A bimetallic system of Pd/CuF2, catalytic in Pd and stoichiometric in Cu, is very efficient and selective for the coupling of fairly hindered aryl silanes with aryl, anisyl, phenylaldehyde, p-cyanophenyl, p-nitrophenyl, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by Cu-II, followed by disproportionation and transmetalation from the Cu-I(aryl) to Pd-II, upon which coupling takes place. Cu-III formed during disproportionation is reduced to Cu-I(aryl) by excess aryl silane, so that the CuF2 system is fully converted into Cu-I(aryl) and used in the coupling. Moreover, no extra source of fluoride is needed. Interesting size selectivity towards coupling is found in competitive reactions of hindered aryl silanes. Easily accessible [PdCl2(IDM)(AsPh3)] (IDM = 1,3-dimethylimidazol-2-ylidene) is by far the best catalyst, and the isolated products are essentially free from As or Pd (<1ppm). The mechanistic aspects of the process have been experimentally examined and discussed.
机译:Pd / CuF2的双金属体系(在Pd中催化并在Cu中以化学计量)非常有效且具有选择性,可将相当受阻的芳基硅烷与常规尺寸的芳基,茴香基,苯甲醛,对氰基苯基,对硝基苯基或吡啶基碘化物偶联。该反应涉及通过Cu-II活化硅烷,然后歧化和从Cu-I(芳基)到Pd-II的重金属转移,然后发生偶联。在歧化过程中形成的Cu-III被过量的芳基硅烷还原为Cu-I(芳基),因此CuF2系统被完全转化为Cu-I(芳基)并用于偶联。而且,不需要额外的氟化物源。在受阻芳基硅烷的竞争反应中发现了对偶联的有趣的尺寸选择性。到目前为止,易于获得的[PdCl2(IDM)(AsPh3)](IDM = 1,3-二甲基咪唑-2-亚基)是最好的催化剂,分离出的产物基本上不含As或Pd(<1ppm)。该过程的机械方面已通过实验检查和讨论。

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