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

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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.