胺-脲介导的通过双重活化的腈氧化物与邻羟基苯乙烯的不对称环加成反应。
Amine-Urea-Mediated Asymmetric Cycloadditions between Nitrile Oxides and o-Hydroxystyrenes by Dual Activation.
机构信息
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano, 380-8553, Japan.
Department of Chemistry, Hyogo College of Medicine, Mukogawa-cho, Nishinomiya, Hyogo, 663-8501, Japan.
出版信息
Angew Chem Int Ed Engl. 2017 Sep 18;56(39):11936-11939. doi: 10.1002/anie.201705662. Epub 2017 Aug 24.
The first example of asymmetric 1,3-dipolar cycloadditions between nitrile oxides and o-hydroxystyrenes, mediated by cinchona-alkaloid-based amine-ureas is reported. The method is based on a dual activation involving both LUMO and HOMO activations. In addition to the stoichiometric asymmetric induction, a catalytic amount of amine-urea enables the cycloadditions to proceed in an enantioselective manner. Computational studies strongly support the HOMO activation of o-hydroxystyrenes and LUMO activation of nitrile oxides by hydrogen-bonding interactions with the Brønsted acid/base bifunctional catalyst.
首次报道了手性金鸡纳生物碱衍生的酰胺-脲催化的腈氧化物与邻羟基苯乙烯的不对称 1,3-偶极环加成反应。该方法基于同时涉及 LUMO 和 HOMO 激活的双重活化。除了化学计量的不对称诱导外，催化量的酰胺-脲还能使环加成反应以对映选择性的方式进行。计算研究强烈支持 Brønsted 酸/碱双功能催化剂通过氢键相互作用对邻羟基苯乙烯的 HOMO 激活和腈氧化物的 LUMO 激活。
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