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Continuous‐Flow Asymmetric Hydrogenation of an Enol Ester by using Supercritical Carbon Dioxide: Ionic Liquids versus Supported Ionic Liquids as the Catalyst Matrix
ChemCatChem ( IF 3.8 ) Pub Date : 2015-06-02 , DOI: 10.1002/cctc.201500295 Ziyun Zhang , Giancarlo Franciò , Walter Leitner
ChemCatChem ( IF 3.8 ) Pub Date : 2015-06-02 , DOI: 10.1002/cctc.201500295 Ziyun Zhang , Giancarlo Franciò , Walter Leitner
The continuous‐flow Rh‐catalyzed asymmetric hydrogenation of the enol ester 1‐(trifluoromethyl)vinyl acetate was investigated by using supercritical carbon dioxide (scCO2) as the mobile phase and either ionic liquids (IL) or supported ionic liquids (SILP) as the catalyst matrix. Three molecular catalysts based on chiral ligands were evaluated. The catalyst based on the phosphine‐phosphoramidite ligand (Sa,Rc)‐Xyl‐QUINAPHOS in combination with the SILP/scCO2 immobilization strategy provided the most effective system under continuous‐flow conditions and gave a remarkably stable performance. During 233 h on stream, high single‐pass conversions (90–70 %), slightly increased enantioselectivity (80–84 % ee), and a turnover number of 70 400 were observed; this turnover number shows a six‐fold increase over that achieved in the IL/scCO2 system with the same catalyst.
中文翻译:
使用超临界二氧化碳进行烯醇酯的连续流不对称加氢:离子液体与负载的离子液体作为催化剂基质
以超临界二氧化碳(scCO 2)为流动相,以离子液体(IL)或负载型离子液体(SILP)为流动相,研究了烯醇酯1-(三氟甲基)乙酸乙烯酯的连续流Rh催化不对称氢化。催化剂基质。评价了三种基于手性配体的分子催化剂。基于膦-亚磷酰胺配体(S a,R c)-Xyl-QUINAPHOS的催化剂与SILP / scCO 2固定化策略相结合,在连续流动条件下提供了最有效的系统,并提供了非常稳定的性能。在运行233小时内,高单程转化率(90–70%),对映选择性略有提高(80–84%ee),观察到营业额为70400;与使用相同催化剂的IL / scCO 2系统相比,该周转率显示出六倍的增长。
更新日期:2015-06-02
中文翻译:
使用超临界二氧化碳进行烯醇酯的连续流不对称加氢:离子液体与负载的离子液体作为催化剂基质
以超临界二氧化碳(scCO 2)为流动相,以离子液体(IL)或负载型离子液体(SILP)为流动相,研究了烯醇酯1-(三氟甲基)乙酸乙烯酯的连续流Rh催化不对称氢化。催化剂基质。评价了三种基于手性配体的分子催化剂。基于膦-亚磷酰胺配体(S a,R c)-Xyl-QUINAPHOS的催化剂与SILP / scCO 2固定化策略相结合,在连续流动条件下提供了最有效的系统,并提供了非常稳定的性能。在运行233小时内,高单程转化率(90–70%),对映选择性略有提高(80–84%ee),观察到营业额为70400;与使用相同催化剂的IL / scCO 2系统相比,该周转率显示出六倍的增长。