Access to P- and Axially Chiral Biaryl Phosphine Oxides by Enantioselective CpxIrIII-Catalyzed C-H Arylations
Access to P- and Axially Chiral Biaryl Phosphine Oxides by Enantioselective CpxIrIII-Catalyzed C-H Arylations
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DOI：
10.1002/anie.201807749
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发表时间：
2018-09-24
影响因子：
16.6
通讯作者：
Cramer, Nicolai
中科院分区：
文献类型：
--
作者：
Jang, Yun-Suk;Wozniak, Lukasz;Cramer, Nicolai
报道了一种含手性环戊二烯(CP-x)配体和邻苯二甲酰基叔亮氨酸为助催化剂的Ir(III)配合物催化氧化膦与邻苯二氮化物的不对称C-H芳基化反应。该方法允许a)手性联芳基膦氧化物，b)对映体选择性地构建空间要求很高的联芳基骨架，以及c)以优异的产率和非对映和对映体选择性选择性地组装轴向和对映体化合物。对映异构化还原提供了具有结构和联芳基骨架的单齿手性磷(III)化合物，在不对称催化中具有重要的配体作用。
An enantioselective C-H arylation of phosphine oxides with o-quinone diazides catalyzed by an iridium(III) complex bearing an atropchiral cyclopentadienyl (Cp-x) 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.