手性亚膦酸酯-咪唑啉N、P双齿配体的设计、合成及其应用研究

In the area of asymmetric catalysis, an appropriate choice of chiral ligand as well as ligand modifications play key roles in fine-tuning the catalytic activities and stereoselectivities of the ensuing catalysis. Recently, people have preparated many excellent chiral ligands. Nonetheless, the development of novel or easily synthesis chiral complexes with excellent catalytic activities.and stereoselectivities still constitutes one of the most challenging and formidable endeavors in the field of asymmetric catalysis.In this project, several types of chiral phosphine-imidazoline N,P bidentate ligangs with facile structural modifications will be synthesized from commercially available starting materials.The applications of the chiral N,P bidentate ligands in the asymmetric catalysis will be investigated. Through choice of ligand backbones, rational modifications of electronic and steric properties of the ligand backbones, as well as optimization of the catalytic reaction conditions, we hope to screen out chiral N,P ligand catalysts with high activities and stereoselectivities.

在不对称催化领域，手性配体的选择及修饰是调控相应催化剂的催化活性和立体选择性的关键因素之一。最近，人们已经合成出了许多优秀的手性配体。尽管如此，发展一类新颖的、易于合成的、高效的催化剂依然是不对称催化领域最具挑战性的研究课题之一。本申请项目拟从易得的、商品化的原料出发，设计合成一类手性亚膦酸酯-咪唑啉N、P双齿配体，探讨该类手性配体在不对称反应中的应用。通过对配体骨架的选择、电子和体积效应的调控以及催化反应条件的优化，筛选出高效和高立体选择性的手性N,P配体催化剂。

高效催化剂的设计合成一直是有机合成领域具有挑战性的研究课题之一。手性膦配体作为催化剂用于不对称催化反应表现出较好的催化活性。近年来氮杂环卡宾配体作为一类重要的有机化合物也备受广大科学家的青睐。基于以上考虑本项目重点开展了手性膦配体的设计合成，并将其应用到了β-取代的烯酮与二乙基锌的1,4-共轭加成反应。另外我们还实现了从廉价易得的起始原料出发经一步反应合成一系列氮杂环卡宾钯化合物的新方法，制备的氮杂环卡宾钯催化剂应用到Suzuki-Miyaura偶联反应、Buchwald-Hartwig胺化反应、插羰反应，均表现出较高的催化活性。