Transition-Metal Catalyzed Disilane Metathesis Reaction of Organosilicon Compounds

过渡金属催化有机硅化合物的乙硅烷复分解反应

• 批准号: 07640707
• 负责人: KABE Yoshio
• 金额: $ 1.54万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640707/
• 关键词: Silicon Compounds; Metathesis; 1,2-Disilacyclobutanes; Zirconocene Complex; 1,2-ジシラシクロブタン; 環状ケイ素化合物; Si-Siメタテシス; トランスメタル化; 環化付加

We found that cyclic disilanes such as 1,2-Disilacyclobutanes underwent palladium-catalyzed Si-Si metathesis to from a dimer (Organometallics, 14,2556(1995)). It was considered which types of cyclic disilanes lead to the Si-Si metathesis reaction as well as a new versatile snthetic method of cyclic disilanes. For the preparation of 1.2-disilacyclobutane, new zirconocene promoted alkyne-coupling reaction of 1,2-alkynyldisilane have been discolsed. However bulky alkoxy groups as erminal substituents of alkynes, which is essential for the zirconocene cpoupling reaction, disturbed the Si-Si metathesis reaction with Pd(PPh3)4 and Pd(CNtBu)2 to afford bissilylpalladium complexes respectively. Furthermore, bissilylpalladium complex react with activated acetylene to give bissilylation products, while the reaction with CpPdAllyl led to the intramolecular sily Heck reaction

我们发现环状二硅烷如1，2-二硅杂环丁烷经历钯催化的Si-Si复分解形成二聚体（Organometallics，14，2556（1995））。讨论了哪种类型的环二硅烷会导致硅-硅复分解反应，以及合成环二硅烷的新方法。在制备1，2-二硅杂环丁烷的研究中，首次报道了茂锆促进的1，2-炔基二硅烷的炔偶联反应。然而，大的烷氧基作为炔的重要取代基，干扰了Pd（PPh_3）_4和Pd（CNTBu）_2的Si-Si复分解反应，分别得到了双硅烷基钯配合物。此外，双硅烷基钯配合物与活性乙炔反应生成双硅烷基化产物，而与CpPd烯丙基反应则发生分子内硅Heck反应

项目成果

W.Ando and Y.Kabe: "The chemistry of organic silicon compounds.vol 2 chap 50" John Wiely and Son Ltd.(Eds.by Z.Rappoport and Y.Apeloig), 61 (1998)

W.Ando 和 Y.Kabe：“有机硅化合物的化学。第 2 卷第 50 章”John Wiely and Son Ltd.（Z.Rappoport 和 Y.Apeloig 编辑），61 (1998)