Synthesis and Reactivity of C-and N-Bound Transitionmetal α-Cyanocarbanions

合成了一种新型的N-键合Cp钌碳负离子配合物，用于Aldol和Michael反应等C-C键形成反应。该配合物可与各种带有吸电子取代基的烯烃反应，得到相应的N-键合钌配合物，其中配体转化为Michael型加合物。此外，还发现含α-烷氧羰基的N-配位钌碳负离子配合物和上述配合物能与缺电子烯烃反应而不损失配位金属。结果表明，金属-邻苯二酚的催化Michael加成反应是由底物的C-H活化产生的，是以离子机理进行的，而不是以金属氢化反应进行的。

A novel N-bound Cp ruthenium carbanion complex was synthesized to apply for the C-C bond formation reactions such as Aldol and Michael reactions. The complex can be reacted with various olefins bearing electron-withdrawing substituents to give the corresponding N-bound ruthenium complex, of which ligand was converted to Michael type adducts. Furthermore, N-bound hydrido ruthenium carbanion complex with α-alkoxycarbonyl group, as well as the complex mentioned above, was found to react with an electron deficient olefin without loss of metal-hydrido. The result suggests that catalytic Michael addition of metal-hydrido, which is generated by C-H activation of substrates, proceeds with ionic mechanism rather than hydrometalation.