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Optimized Immobilization Strategy for Dirhodium(II) Carboxylate Catalysts for C-H Functionalization and Their Implementation in a Packed Bed Flow Reactor.
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2020-06-01 , DOI: 10.1002/anie.202005381
Taylor A Hatridge 1 , Wenbin Liu 2 , Chun-Jae Yoo 1 , Huw M L Davies 2 , Christopher W Jones 1
Affiliation  

Herein we demonstrate a packed bed flow reactor capable of achieving highly regio‐ and stereoselective C−H functionalization reactions using a newly developed Rh2(S‐2‐Cl‐5‐CF3TPCP)4 catalyst. To optimize the immobilized dirhodium catalyst employed in the flow reactor, we systematically study both (i) the effects of ligand immobilization position, demonstrating the critical factor that the catalyst‐support attachment location can have on the catalyst performance, and (ii) silica support mesopore length, demonstrating that decreasing diffusional limitations leads to increased accessibility of the active site and higher catalyst turnover frequency. We employ the immobilized dirhodium catalyst in a simple packed bed flow reactor achieving comparable yields and levels of enantioselectivity to the homogeneous catalyst employed in batch and maintain this performance over ten catalyst recycles.

中文翻译:

用于羧酸功能化的羧酸二甲酯(II)催化剂的最佳固定化策略及其在填充床流动反应器中的实施

在这里,我们演示了一种填充床流反应器,该反应器能够使用新开发的Rh 2S -2-Cl-5-CF 3 TPCP)4实现高度区域选择性和立体选择性CH功能化反应4催化剂。为了优化在流动反应器中使用的固定的铱催化剂,我们系统地研究了(i)配体固定位置的影响,证明了催化剂-载体连接位置对催化剂性能的影响,以及(ii)二氧化硅载体中孔长度,表明减小的扩散限制导致活性位点的可及性增加和催化剂转换频率较高。我们在简单的填充床流动反应器中使用了固定的铱催化剂,获得了与批量使用的均相催化剂相当的收率和对映选择性,并在十次催化剂循环中保持了这一性能。
更新日期:2020-06-01
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