Silyl-Group-Directed Linear-Selective Allylation of Carbonyl Compounds with Trisubstituted Allylboronates Using a Copper(I) Catalyst
Silyl-Group-Directed Linear-Selective Allylation of Carbonyl Compounds with Trisubstituted Allylboronates Using a Copper(I) Catalyst
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DOI：
10.1021/acscatal.9b05408
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发表时间：
2020-02-21
期刊：
影响因子：
12.9
通讯作者：
Ito, Hajime
中科院分区：
文献类型：
--
作者：
Iwamoto, Hiroaki;Hayashi, Yuta;Ito, Hajime
利用硅基的电子和空间效应，实现了铜(I)催化羰基化合物与三取代硼基烯丙酸酯的线性选择性烯丙基化。这个反应提供了立体的三取代全烯丙醇衍生物，该衍生物具有合成上有用的烯基硅烷部分。计算结果表明，硅基导向基团在热力学上稳定了位阻烯丙基铜(I)中间体，并通过降低过渡态的能量，在动力学上促进了线性产物的羰基烯丙基化路径。
A copper(I)-catalyzed linear-selective allylation of carbonyl compounds with trisubstituted allylboronates has been achieved by capitalizing on the electronic and steric effects of silyl groups. This reaction provides stereodefined trisubstituted homoallyl alcohol derivatives that bear a synthetically useful alkenyl silane moiety. The results of a computational study suggested that the silyl directing group thermodynamically stabilizes the sterically hindered allylcopper(I) intermediate and kinetically facilitates the carbonyl allylation path for the linear product by lowering the energy of its transition state.