Liang Xin-Shen, Li Rui-Dong, Wang Xiao-Chen
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of, Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.
Angew Chem Int Ed Engl. 2019 Sep 23;58(39):13885-13889. doi: 10.1002/anie.201907943. Epub 2019 Aug 14.
We have developed a method for the highly diastereo- and enantioselective construction of 2,3-dihydrobenzofurans bearing tetrasubstituted carbon stereocenters by means of annulation reactions between carbenes and 2-iminyl- or 2-acyl-substituted phenols through catalysis by readily accessible copper(I)/bisoxazoline catalysts under mild conditions. These reactions feature a unique mechanism in which the copper catalyst serves a dual function: first it reacts with the diazo compound to generate a metal carbene, and second, upon formation of an oxonium ylide, it acts as a Lewis acid to activate the imine or ketone for diastereo- and enantioselective cyclization.
我们已经开发出一种方法，可通过在易于获得的铜（I）/双恶唑啉催化剂催化下，在温和条件下使卡宾与2-亚氨基或2-酰基取代的酚发生环化反应，以高非对映选择性和对映选择性构建带有四取代碳立体中心的2,3-二氢苯并呋喃。这些反应具有独特的机理，其中铜催化剂具有双重功能：首先它与重氮化合物反应生成金属卡宾，其次，在氧鎓叶立德形成后，它作为路易斯酸活化亚胺或酮以进行非对映选择性和对映选择性环化。
