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首页> 外文期刊>Catalysis science & technology >Asymmetric epoxidation of unfunctionalized olefins accelerated by thermoresponsive self-assemblies in aqueous systems
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Asymmetric epoxidation of unfunctionalized olefins accelerated by thermoresponsive self-assemblies in aqueous systems

机译：unfunctionalized烯烃的不对称环氧化作用加速了thermoresponsive自组装在水系统

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摘要

A novel thermoresponsive surfactant-type chiral salen Mn-III catalyst was developed by axially grafting "smart" poly(N-isopropylacrylamide) (PNIPAAm) onto the metal center of a neat chiral salen Mn-III complex. Characterization data suggests thermoresponsive micellization behavior of the obtained catalyst in water. The chiral metallomicellar catalyst acted as a nanoreactor to carry out asymmetric epoxidation of unfunctionalized olefins in water and dramatically accelerated reaction rates. Outstanding catalytic efficiency was observed in the nanoreactor system. In particular, quantitative conversion (99%) of styrene with high enantioselectivity (39%) was achieved over 0.8 mol% of the catalyst within 3 min, giving an unprecedented TOF value (2.48 x 10(3) h(-1)) which is significantly higher than that obtained over previously reported homogeneous or heterogeneous systems. Moreover, the catalyst could be easily recovered by thermocontrolled separation and reused with high activity for five cycles.
机译：一种新型thermoresponsive活化剂手性的塞伦Mn-III催化剂是由轴向嫁接“智能”保利(N-isopropylacrylamide)(PNIPAAm)到一个整洁的手性的金属中心塞伦Mn-III复杂。表明thermoresponsive胶束化行为得到的催化剂在水里。充当了nanoreactor metallomicellar催化剂进行的不对称环氧化作用在水和unfunctionalized烯烃大大加快了反应速率。优秀的催化效率被观察到nanoreactor系统。定量转换的苯乙烯(99%)实现高选择性(39%)0.8 mol % 3分钟内的催化剂,给一个前所未有的TOF值(2.48 x 10 (3) h (1))这是明显高于获得吗在之前报道齐次或异构系统。可以很容易地恢复了thermocontrolled吗分离和重用五高的活动周期。

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