Syntheses of functional molecules using highly strained sp-carbon atoms in unsaturated cyclic organometallic compounds

使用不饱和环状有机金属化合物中高张力sp-碳原子合成功能分子

• 批准号: 22350022
• 负责人: SUZUKI Noriyuki
• 金额: $ 12.31万
• 依托单位: Sophia University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2010
• 资助国家: 日本
• 起止时间: 2010-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-22350022/
• 关键词: ジルコニウム; 環状アレン; カルベン; エンイン; 複素環; イオウ; 窒素; 環状アルキン; 有機金属化合物; アルキニルイミン; クムレン; 炭素-炭素結合生成

We studied on the synthesis, structure and reactivity on conjugated five-membered alkyne complexes derived from group 4 metals and cumulene derivatives. We also investigated five-membered cyclic allenes that are formed from conjugated enynes on the property of highly strained sp carbon in the cyclic unsaturated compounds. It is difficult to isolate one of the isomers of E/Z-[5]cumulenes because of low barrier for isomerization. We succeeded in isolation of the E-isomer and trapping the Z-isomer as a metal complex. Haptotropic interconversion between cyclic structure and eta2-coordination was also examined and the effect of steric environment of the substituents were found. We have found facile preparative method of five-membered cyclic allene from conjugated enyne.

研究了4族金属和积云烯衍生物共轭五元炔配合物的合成、结构和反应性。我们还研究了由共轭烯形成的五元环烯对环不饱和化合物中高应变sp碳的性质。由于E/Z-[5]的异构化势垒较低，很难分离出其同分异构体。我们成功地分离了e -异构体，并将z -异构体作为金属配合物捕获。研究了环结构与乙二配位之间的触觉转换，发现了取代基空间环境的影响。我们发现了一种由共轭烯制备五元环烯的简便方法。

项目成果

[5]クムレン類のジルコニウム錯体におけるハプトトロピックな配位挙動

[5] 积烯锆配合物的触变配位行为

• 发表时间: 2012
• 作者: 吉谷孝雄;鈴木教之;増山芳郎
• 通讯作者: 増山芳郎

Metallacyclic Compounds Derived from Group 4 Metals and [n]Cumulenes (n=3,5)

源自第 4 族金属和 [n] 积烯 (n=3,5) 的金属环化合物

• 发表时间: 2010
• 作者: T.Masuyama;M.Suzuki;et al.;Noriyuki Suzuki
• 通讯作者: Noriyuki Suzuki

4C8-19 塩化スズ(II)を触媒とする1-置換プロパルギルアルコールと炭素求核剤の反応

4C8-19 氯化锡(II)催化下1-取代的炔丙醇与碳亲核试剂的反应

• 发表时间: 2011
• 作者: Y.Funahashi;T.Toyama;K.Yoshii;T.Nishikawa;M.Kishida;Y.Kajita;T.Inomata;T.Ozawa;Y.Wasada-Tsutsui;H.Masuda;勝間田匠・井川善也・古田弘幸;Takashi Koike and Munetaka Akita;林美樹・鈴木教之・増山芳郎
• 通讯作者: 林美樹・鈴木教之・増山芳郎

Five-membered metallacycloalkynes formed from group 4 metals and [n]cumulene (n = 3,5) ligands

• DOI: 10.1016/j.ccr.2009.12.016
• 发表时间: 2010-06
• 期刊: Coordination Chemistry Reviews
• 影响因子: 20.6
• 作者: N. Suzuki;D. Hashizume

Synthesis of Seven-membered Cyclic Allenes That Consist of Organometallic Compounds

有机金属化合物七元环烯的合成

• 发表时间: 2013
• 作者: Noriyuki Suzuki;Takashi Tsuchiya;Yoshiro Masuyama
• 通讯作者: Yoshiro Masuyama