Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-3215.
Chemistry. 2014 Jan 13;20(3):745-51. doi: 10.1002/chem.201303146. Epub 2013 Dec 6.
An improved synthesis of a novel class of bidentate (P,N) ligands is presented, the structures of which are characterized by three distinct elements of chirality. The stereoselective installation of the elements of central chirality (at the benzylic carbon and the phosphorus atom) depends on the size of the phosphorus substituent. Thermal inversion of the phosphorus center has been studied experimentally and further correlated by DFT calculations. The potential of these ligands and the role of the phosphorus atom in the asymmetric α-arylation of aldehydes (Pd) and hydrogenation of allylic alcohols (Ir) have also been investigated.
呈现了一类新型双齿 (P,N) 配体的改进合成方法，其结构的特点是具有三个不同的手性元素。手性中心元素（苄基碳和磷原子）的立体选择性安装取决于磷取代基的大小。磷中心的热反转已通过实验和进一步通过 DFT 计算进行了相关研究。还研究了这些配体的潜力以及磷原子在醛的不对称 α-芳基化（Pd）和烯丙醇的氢化（Ir）中的作用。
