捕获 NHC 封端环糊精中的单体 (L)CuH：空腔控制的α,β-不饱和酮的选择性硅氢化反应。
Capturing the Monomeric (L)CuH in NHC-Capped Cyclodextrin: Cavity-Controlled Chemoselective Hydrosilylation of α,β-Unsaturated Ketones.
机构信息
Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire (IPCM), UMR 8232, 4, place Jussieu, 75005, Paris, France.
Institute of Condensed Matter and Nanosciences (IMCN), Molecules, Solids and Reactivity (MOST), Université Catholique de Louvain (UCL), Place Louis Pasteur 1, 1348, Louvain-La-Neuve, Belgium.
出版信息
Angew Chem Int Ed Engl. 2020 May 4;59(19):7591-7597. doi: 10.1002/anie.202001733. Epub 2020 Mar 10.
The encapsulation of copper inside a cyclodextrin capped with an N-heterocyclic carbene (ICyD) allowed both to catch the elusive monomeric (L)CuH and a cavity-controlled chemoselective copper-catalyzed hydrosilylation of α,β-unsaturated ketones. Remarkably, (α-ICyD)CuCl promoted the 1,2-addition exclusively, while (β-ICyD)CuCl produced the fully reduced product. The chemoselectivity is controlled by the size of the cavity and weak interactions between the substrate and internal C-H bonds of the cyclodextrin.
将铜封装在带有 N-杂环卡宾 (ICyD) 的环糊精中，既可以捕获难以捉摸的单体 (L)CuH，又可以控制腔选择性地催化α,β-不饱和酮的铜催化氢化硅烷化反应。值得注意的是，(α-ICyD)CuCl 促进了 1,2-加成反应，而 (β-ICyD)CuCl 则生成了完全还原的产物。这种化学选择性受空腔大小和底物与环糊精内部 C-H 键之间弱相互作用的控制。
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