Jang Yun-Suk, Woźniak Łukasz, Pedroni Julia, Cramer Nicolai
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, CH-, 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2018 Sep 24;57(39):12901-12905. doi: 10.1002/anie.201807749. Epub 2018 Aug 29.
An enantioselective C-H arylation of phosphine oxides with o-quinone diazides catalyzed by an iridium(III) complex bearing an atropchiral cyclopentadienyl (Cp ) ligand and phthaloyl tert-leucine as co-catalyst is reported. The method allows access to a) P-chiral biaryl phosphine oxides, b) atropo-enantioselective construction of sterically demanding biaryl backbones, and also c) selective assembly of axial and P-chiral compounds in excellent yields and diastereo- and enantioselectivities. Enantiospecific reductions provide monodentate chiral phosphorus(III) compounds having structures and biaryl backbones with proven importance as ligands in asymmetric catalysis.
报道了一种由带有阻转手性环戊二烯基（Cp）配体的铱（III）配合物和邻苯二甲酰叔亮氨酸作为共催化剂催化的氧化膦与邻醌二氮烯的对映选择性C-H芳基化反应。该方法能够实现：a）P-手性联芳基氧化膦的合成；b）空间位阻较大的联芳基骨架的阻转对映选择性构建；以及c）以优异的产率、非对映选择性和对映选择性选择性组装轴向和P-手性化合物。对映体特异性还原提供了具有特定结构和联芳基骨架的单齿手性磷（III）化合物，这些化合物在不对称催化中作为配体具有重要意义。
