手性含硫配体的设计合成及在不对称转移氢化中的应用
Design and Synthesis of Chiral Sulfur-Containing Ligands and their Applications in Asymmetric Transfer Hydrogenation
摘要
优秀的手性配体是实现高对映选择性不对称催化的关键。与传统的含膦、氮和氧的手性配体相比，手性含硫配体的研究相对较少，一个重要的原因是习惯上认为硫会使催化剂中毒。然而，硫原子有丰富的电子性质和结构特性，近年来手性含硫配体的开发与应用研究已渐露头角。本论文的研究集中在新型手性含硫配体的设计合成及在不对称转移氢化中的应用，包括以下四部分内容： 1.手性硫醚三齿配体的设计合成、结构表征与催化性能研究。以2-苯硫基邻苯甲醛为原料合成了手性硫醚三齿配体C6N(NH)S和C6(NH)2S，获得了C6N(NH)S的单晶结构，并将硫醚配体分别与钌、铑或铱络合物组合的催化体系，应用在苯丙酮的不对称催化还原中，得到... Chiral ligands have been known to play an important role in transition metal complexes-catalyzed asymmetric reactions. Sulfur-containing based chiral mixed ligands have received much less attention than the ligands with P, N or O as donor atoms. A possible reason is sulfur has a tendency to poison heterogeneous catalysts. The key structural features of sulfur atom exhibit very rich coordination ch...