Reactive & Functional Polymers ( IF 4.5 ) Pub Date : 2020-05-05 , DOI: 10.1016/j.reactfunctpolym.2020.104615 Jan Bartáček , Jiří Váňa , Pavel Drabina , Jan Svoboda , Martin Kocúrik , Miloš Sedlák
The development of recoverable catalysts based on the combination of synthetically demanding ligands with transition metals attracts a lot of attention, especially from the environmental point of view. In this paper, we describe the preparation of a recoverable polystyrene supported chiral palladium catalyst based on PyOx ligand suitable for asymmetric 1,4-addition of arylboronic acids to cyclic 3-substituted five- and six-membered enones. In the reaction, all‑carbon quaternary stereocenters are formed with a high level of enantioselectivity (up to 91% ee) and conversion (up to 99%). The catalyst was used in 6 cycles with no loss of enantioselectivity and only a small decrease in conversion. A solution of the problems associated with the transition from homogeneous to heterogeneous catalytic systems is discussed.
中文翻译:
可回收的聚苯乙烯负载钯催化剂,用于通过芳基硼酸与环烯酮的不对称1,4-加成反应来构建全碳四元立体中心
基于合成要求的配体与过渡金属的结合物的可回收催化剂的开发引起了很多关注,特别是从环境的角度来看。在本文中,我们描述了基于PyOx配体的可回收聚苯乙烯负载的手性钯催化剂的制备,该催化剂适用于芳基硼酸向环状3取代的五元和六元烯酮的不对称1,4-加成。在该反应中,形成的全碳四元立体中心具有高水平的对映选择性(高达91%ee)和转化率(高达99%)。该催化剂以6个循环使用,没有损失对映选择性,并且转化率仅小幅下降。讨论了与从均相催化系统过渡到非均相催化系统有关的问题的解决方案。