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Inverted supercritical carbon dioxide/aqueous biphasic media for rhodium-catalyzed hydrogenation reactions

机译:倒置超临界二氧化碳/水性双相培养基,用于铑催化的氢化反应

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摘要

An inverted supercritical carbon dioxide (scCO(2))/aqueous biphasic system has been used as reaction media for Rh-catalysed hydrogenation of polar substrates. Chiral and achiral CO2-philic catalysts were efficiently immobilised in scCO(2) as the stationary phase, while the polar substrates and products were contained in water as the mobile phase. Notably, product separation and catalyst recycling were conducted without depressurisation of the autoclave. The catalyst phase was reused several times with high conversion and product recovery of more than 85%. Loss of rhodium and phosphorus by leaching were found to be below the detection limit after the first two cycles in the majority of repetitive experiments. The reaction conditions were optimised with a minimum of experiments by using a simplex algorithm in a sequential optimisation. Total turn-over numbers (TTNs) of up to 1600, turnover frequencies (TOFs) of up to 340 h(-1) and ee's up to 99 % were obtained in repetitive batch operations. The scope of the devised catalytic system has been investigated and a semicontinuous reaction setup has been implemented. The chiral ligand (R,S)-3-(HF6)-F-2-BINAPHOS allowed highly enantioselective hydrogenation of itaconic acid and methyl-2-acetamidoacrylate combined with a considerable catalyst stability in these reaction media.
机译:倒置超临界二氧化碳(SCCO(2))/水性双相体系已被用作极性衬底的RH催化氢化的反应介质。作为固定相,手性和成立的CO2-素催化剂在SCCO(2)中有效地固定在SCCO(2)中,而极性衬底和产物作为流动相中含有水。值得注意的是,进行产物分离和催化剂再循环而不会对高压釜减压进行。用高转化率和产物回收率重复用几次催化剂相,超过85%。通过浸出丧失铑和磷的损失在大多数重复实验中的前两个循环后低于检测限。通过在顺序优化中使用单独的算法,通过使用单纯形算法进行优化反应条件。在重复批量操作中获得了高达1600,最高340小时(-1)和EE高达99%的营业额频率(TOF)的总转向数量(TTN)和EE高达99%。已经研究了设计的催化系统的范围,并实施了半连续反应设置。手性配体(R,S)-3-(HF6)-F-2-BINAphOS允许高度映射液体溶解的衣康酸和甲基-2-乙酰胺丙烯酸酯,在这些反应介质中加入具有相当大的催化剂稳定性。

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