Liu Can, Zhu Xianjin, Zhang Pengxiang, Yang Haijun, Zhu Changjin, Fu Hua
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, China; Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, China.
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, China.
iScience. 2018 Dec 21;10:11-22. doi: 10.1016/j.isci.2018.11.018. Epub 2018 Nov 14.
In transition metal-catalyzed asymmetric synthesis, enantioselectivity strongly depends on the structures of chiral ligands, so the development of new chiral ligands is crucial. Here, an efficient and highly enantioselective palladium-catalyzed intramolecular hydroarylation has been developed, and a new kind of N-heterocycles, 1H-pyrazolo[5,1-a]isoindol-2(8H)-ones containing a quaternary stereocenter, was prepared in high yields and excellent enantiomeric excess values. The reaction was effectively catalyzed by palladium-diphosphine complexes with numerous functional group tolerance, in which the newly developed axially chiral cyclic diphosphine ligands played key roles in the reactivity and enantioselectivity of the substrates. We believe that the cyclic diphosphine ligands with adjustable dihedral angles will find wide application in asymmetric synthesis.
在过渡金属催化的不对称合成中，对映选择性强烈依赖于手性配体的结构，因此开发新型手性配体至关重要。在此，已开发出一种高效且对映选择性高的钯催化分子内氢芳基化反应，并以高收率和优异的对映体过量值制备了一种新型含季立体中心的N-杂环化合物1H-吡唑并[5,1-a]异吲哚-2(8H)-酮。该反应由具有多种官能团耐受性的钯-二膦配合物有效催化，其中新开发的轴向手性环状二膦配体在底物的反应性和对映选择性中起关键作用。我们相信，具有可调节二面角的环状二膦配体将在不对称合成中得到广泛应用。
