Design and Development of New Catalytic System Using Ate Complexes as Key-Species

本文提出了一种在镍催化剂作用下格氏试剂与烷基氯、溴和对甲苯磺酸酯的交叉偶联反应的新方法。该反应通过使用伯和仲烷基或芳基卤化镁在温和条件下有效地进行。使用1，3-丁二烯代替膦配体作为添加剂是获得交叉偶联产物高产率的关键。我们还首次报道了金属催化的烷基氟与格氏试剂的交叉偶联反应。这些反应有效地进行伯烷基氟化物和各种格氏试剂在温和的条件下，在镍或铜盐的存在下。在镍催化剂的辅助下，发展了一种高区域选择性的双烯、氯硅烷和格氏试剂四组分偶联反应的新方法。该反应提供具有烯丙基硅烷单元的1，6-二烯。本研究提供了第一个使用后过渡金属催化的氯硅烷的C-Si键形成反应的例子。另一方面，我们还开发了一种新的方法，用于钯催化的区域选择性的两个C-Si键和一个C-C键的形成反应，使用氯硅烷。该反应通过使用芳基或烯丙基取代的氯硅烷立体选择性地进行，产生具有两个烯丙基硅烷单元的1，6-辛二烯。

A novel method for cross-coupling reaction of Grignard reagents with alkyl chlorides, bromides, and tosylates has been developed with the aid of Ni catalysts. This reaction proceeds efficiently by the use of primary and secondary alkyl-or arylmagnesium halides under mild conditions. The use of 1,3-butadiene as an additive instead of phosphine ligands is the key to attain high yields of the cross-coupling products. We also revealed the first example of metal-catalyzed cross-coupling reaction of alkyl fluorides with Grignard reagents. These reactions proceed efficiently between primary alkyl fluorides and various Grignard reagents under mild conditions in the presence of nickel or copper salts. Anew method for a highly regioselective four-component coupling reaction of 2 molecules of dienes, a chlorosilane and a Grignard reagent has been developed with the aid of nickel catalysts. This reaction provides 1,6-dienes having an allylsilane unit. This study provides the first example of C-Si bond-forming reaction using chlorosilanes catalyzed by late transition metals. On the other hand, we have also developed a new method for Pd-catalyzed regioselective two C-Si bonds and one C-C bond forming reaction using chlorosilane. This reaction proceeds stereoselectively by the use of aryl or allyl substituted chlorosilanes giving rise to 1, 6-octadienes having two allylsilane unit.