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

C-和 N-键过渡金属 α-氰基碳负离子的合成和反应活性

• 批准号: 13450371
• 负责人: NAOTA Takeshi
• 金额: $ 4.54万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450371/
• 关键词: cyanocarbanion; ruthenium; Michael reaction; Aldol reaction; α-シアノカルバニオン

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.

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。

项目成果

Takeshi Naota, Akio Tannna, Shigeaki Kamuro, ShuuIchi Murahashi: "Mechanism of the Interconversions between C-and N-Bound Transition Metal α-Cyanocarbanions"J. Am. Chem. Soc.. 124. 6842-6843 (2002)

Takeshi Naota、Akio Tanna、Shigeaki Kamuro、ShuuIchi Murahashi：“C 和 N 结合过渡金属 α-氰基碳阴离子之间的相互转化机制”J. Soc. 124。 6842-6843

Naota Takeshi, Tannna Akio, Kamuro Shigeaki, Murahashi Shun-Ichi: "Mechanism of the Interconversions between C- and N-Bound Transition Metal α-Cyanocarbanions"J.Am.Chem.Soc.. 124. 6842-6843 (2002)

Naota Takeshi、Tanna Akio、Kamuro Shigeaki、Murahashi Shun-Ichi：“C 和 N 结合过渡金属 α-氰碳阴离子之间的相互转化机制” J.Am.Chem.Soc.. 124. 6842-6843 (2002)

Naota Takeshi, Komiya Naruyoshi: "Jikken Kagaku Koza, 5th ed, vol 17 (in Japanese)"Maruzen (in press).

Naota Takeshi、Komiya Naruyoshi：“Jikken Kagaku Koza，第 5 版，第 17 卷（日文）”Maruzen（正在印刷中）。

Murahashi Shun-Ichi, Takaya Hikaru, Naota Takeshi: "Ruthenium Catalysis in Organic Synthesis"Pure Appl.Chem.. 74. 19-24 (2002)

Murahashi Shun-Ichi、Takaya Hikaru、Naota Takeshi：“有机合成中的钌催化”Pure Appl.Chem.. 74. 19-24 (2002)

直田 健, 小宮成義: "有機合成のための触媒反応103"東京化学同人. 22-25 (2004)

Ken Naota、Shigeyoshi Komiya：“有机合成的催化反应 103”东京化学同人。