用于烯烃氢甲酰化反应的具有强π-受体含膦多孔有机聚合物的高活性铑催化剂。

Highly Active Rh Catalysts with Strong π-Acceptor Phosphine-Containing Porous Organic Polymers for Alkene Hydroformylation.

作者信息

Wu Miaojiang, Gao Guang, Yang Chao, Sun Peng, Li Fuwei

机构信息

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China.

University of Chinese Academy of Sciences, Beijing 100049, China.

出版信息

J Org Chem. 2023 Apr 21;88(8):5059-5068. doi: 10.1021/acs.joc.2c02105. Epub 2022 Nov 7.

DOI:10.1021/acs.joc.2c02105

PMID:36343284

Abstract

Phosphine-containing porous organic polymers (phosphine-POPs) are a kind of potential catalyst support for alkene hydroformylation. However, the synthesis of phosphine-POPs with strong π-acceptor is still a challenge. Herein, we report the synthesis of phosphine-POPs with different π-acceptor properties [POL-P(Pyr), CPOL-BPa&PPh-15, and CPOL-BP&PPh-15] and evaluated their performances as ligands to coordinate with Rh(acac)(CO) for hydroformylation of alkenes. We found that the Rh center with stronger π-acceptor phosphine-POPs showed better catalytic performance. Rh/CPOL-BPa&PPh-15 with strong π-acceptor bidentate phosphoramidites showed obviously higher activity and regioselectivity (TON = 7.5 × 10, l/b = 26.1) than Rh/CPOL-BP&PPh-15 (TON = 5.3 × 10, l/b = 5.0) with weaker π-acceptor bidentate phosphonites. Particularly, the TON of the hydroformylation reached 27.7 × 10 upon using Rh/POL-P(Pyr) which possessed tris(1-pyrrolyl)phosphane coordination sites. Overall, our study provides an orientation to design phosphine-POPs for hydroformylation reactions.

摘要

含膦多孔有机聚合物（膦基-POPs）是一类用于烯烃氢甲酰化反应的潜在催化剂载体。然而，合成具有强π-受体的膦基-POPs仍然是一项挑战。在此，我们报道了具有不同π-受体性质的膦基-POPs【POL-P(Pyr)、CPOL-BPa&PPh-15和CPOL-BP&PPh-15】的合成，并评估了它们作为配体与Rh(acac)(CO)配位用于烯烃氢甲酰化反应的性能。我们发现，具有较强π-受体的膦基-POPs的Rh中心表现出更好的催化性能。具有强π-受体双齿磷酰胺酯的Rh/CPOL-BPa&PPh-15的活性和区域选择性（TON = 7.5 × 10，l/b = 26.1）明显高于具有较弱π-受体双齿亚膦酸酯的Rh/CPOL-BP&PPh-15（TON = 5.3 × 10，l/b = 5.0）。特别地，使用具有三(1-吡咯基)膦配位位点的Rh/POL-P(Pyr)时，氢甲酰化反应的TON达到27.7 × 10。总体而言，我们的研究为设计用于氢甲酰化反应的膦基-POPs提供了方向。