Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8551, Japan.
Present address: Department of Chemistry, Faculty of Science, Tokyo University of Science, Tokyo, 162-8601, Japan.
Angew Chem Int Ed Engl. 2018 Feb 19;57(8):2130-2133. doi: 10.1002/anie.201711726. Epub 2018 Jan 26.
A conceptually new method for the catalytic electrophilic activation of aromatic carbonyl substrates, by utilizing donor-acceptor interactions between an electron-deficient macrocyclic boronic ester host ([2+2] ) and an aromatic carbonyl guest substrate, was realized. In the presence of a catalytic amount of [2+2] , dramatic acceleration of the nucleophilic addition of a ketene silyl acetal towards either electron-rich aromatic aldehydes or ketones was achieved. Several control experiments confirmed that inclusion of the aromatic substrates within [2+2] , through efficient donor-acceptor interactions, is essential for the acceleration of the reaction.
实现了一种通过利用缺电子大环硼酸酯主体([2+2])与芳香羰基客体底物之间的供体-受体相互作用，对芳香族羰基底物进行催化亲电活化的新概念方法。在[2+2]的催化量存在下，实现了烯醇硅缩醛对富电子芳香醛或酮的亲核加成的显著加速。几个对照实验证实，通过有效的供体-受体相互作用将芳香底物包含在[2+2]中对于反应的加速是必不可少的。
