Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon
Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon
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DOI：
10.1016/j.tet.2020.131493
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发表时间：
2020-10-02
期刊：
影响因子：
2.1
通讯作者：
Korenaga, Toshinobu
中科院分区：
文献类型：
--
作者：
Horino, Yoshikazu;Ishibashi, Mayo;Korenaga, Toshinobu
在CsF存在下，γ-甲硅烷基化的乙酸烯丙酯与水的钯催化反应诱导硅上取代基的先前前所未有的1，2-移位以原位产生烯丙基硅烷。当使用具有氟取代基的贫电子膦配体时，钯的催化活性增加。进一步的研究表明，基团从硅上迁移的倾向性顺序为PhC C，烯丙基> Bn > Ph，乙烯基>烷基（Me，Et）。采用密度泛函理论研究了反应机理。最后，Hosomi-Sakurai型烯丙基化醛原位生成的α，γ-二取代烯丙基硅烷也进行了研究。(C)2020爱思唯尔有限公司保留所有权利。
The palladium-catalyzed reaction of gamma-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi-Sakurai-type allylation of aldehydes with in situ-generated alpha,gamma-disubstituted allylsilanes was also investigated. (C) 2020 Elsevier Ltd. All rights reserved.