Kakiuchi Fumitoshi, Tsuchiya Kazuyuki, Matsumoto Mitsutaka, Mizushima Eiichiro, Chatani Naoto
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2004 Oct 13;126(40):12792-3. doi: 10.1021/ja047040d.
Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction.
钌催化苄基位置的sp3 C-H键与硅烷进行硅氢化反应生成苄基硅烷。对于该硅氢化反应,Ru3(CO)12配合物表现出高催化活性。该硅氢化反应选择性地在甲基C-H键处进行。对于该硅氢化反应,吡啶基和吡唑基以及腙中的亚氨基可作为导向基团。几种含三乙基硅烷、二甲基苯基硅烷、叔丁基二甲基硅烷和三苯基硅烷的硅烷可用作硅烷化试剂。sp2氮原子与钌配合物的配位对于实现该硅氢化反应很重要。