本文選題：J?rgensen　切入點(diǎn)：Hayashi　出處：《西南大學(xué)》2016年碩士論文

【摘要】：近年來(lái)迅速發(fā)展起來(lái)的有機(jī)小分子催化劑因其具有環(huán)境友好且無(wú)金屬危害等優(yōu)勢(shì),已成為不對(duì)稱催化領(lǐng)域的研究熱點(diǎn)之一。然而,昂貴有機(jī)手性催化劑的回收策略及高催化性能的非均相催化體系,特別是多組分非均相催化體系,成為研究者們面對(duì)的新挑戰(zhàn)。本文基于綠色化學(xué)理念,構(gòu)建核殼和空殼納米微球形貌負(fù)載J?rgensen Hayashi有機(jī)催化劑,改善有機(jī)催化劑的催化效能,實(shí)現(xiàn)催化性能優(yōu)良的非均相不對(duì)稱串聯(lián)反應(yīng)。本論文以Boc-L-脯氨酸為初始原料,通過(guò)甲基化、親核加成、脫保護(hù)和取代等步驟合成脯氨酸衍生的J?rgensen Hayashi催化劑ProTMS,用三類不同制備方法和工藝條件分別制備聚苯乙烯共聚物負(fù)載有機(jī)手性催化劑Poly(St/ProTMS)、聚苯乙烯納米共聚物為內(nèi)核的核殼形貌負(fù)載有機(jī)催化劑PS@ProTMS CSNs和空殼納米聚合物負(fù)載有機(jī)催化劑AM/ProTMS HNs。并用掃描電鏡(SEM)、熱重分析(TG)、N2吸附-脫附比表面積、透射電鏡(TEM)等分析測(cè)試手段對(duì)三種不同類型的負(fù)載有機(jī)手性催化劑的組成、結(jié)構(gòu)和形貌等進(jìn)行了表征。以反式-硝基苯乙烯、丙醛和肉桂醛三組分的不對(duì)稱串聯(lián)加成反應(yīng)為模板,探索了不同反應(yīng)溫度、溶劑、催化劑用量等條件對(duì)Michael/Michael/aldol不對(duì)稱串聯(lián)催化反應(yīng)性能的影響,篩選出了Michael/Michael/aldol串聯(lián)催化反應(yīng)的最佳反應(yīng)條件。催化劑AM/ProTMS HNs(4/b)在Michael/Michael/aldol不對(duì)稱串聯(lián)催化反應(yīng)中的催化性能最好,取得與其均相催化反應(yīng)相當(dāng)?shù)拇呋阅�。在各類衍生物的不�?duì)稱串聯(lián)加成反應(yīng),產(chǎn)率為32 60%,dr=80 93/7 20,對(duì)映選擇性≥99%ee。反應(yīng)結(jié)束后,通過(guò)簡(jiǎn)單的過(guò)濾或離心實(shí)現(xiàn)催化劑的回收,在催化劑的重復(fù)使用過(guò)程中,仍能保持原先的立體選擇性,但產(chǎn)物的產(chǎn)率逐漸下降。
[Abstract]:In recent years, the rapidly developed organic small molecule catalysts have become one of the research hotspots in the field of asymmetric catalysis because of their advantages of being environmentally friendly and free of metal harm. The recovery strategy of expensive organic chiral catalysts and heterogeneous catalytic systems with high catalytic performance, especially multicomponent heterogeneous catalytic systems, have become a new challenge for researchers. The morphology of core-shell and hollow shell nanospheres loaded with J? Rgensen / Hayashi organic catalyst can improve the catalytic performance of organic catalyst and realize heterogeneous asymmetric series reaction with excellent catalytic performance. In this paper, Boc-L- proline was used as the initial raw material, and nucleophilic addition was carried out by methylation, nucleophilic addition, methylation and nucleophilic addition of Boc-L-proline. Synthesis of proline derived J? Three kinds of preparation methods and process conditions for the preparation of polystyrene copolymer supported organic chiral catalyst, PS@ProTMS CSNs and hollow shell, respectively, with polystyrene nanocopolymers as core, polystyrene nanocopolymers as core, supported organic catalyst PS@ProTMS CSNs and hollow shell, respectively, were prepared by using three kinds of different preparation methods and process conditions. Nano-polymer supported organic catalyst AM/ProTMS HNs was used for thermogravimetric analysis of the specific surface area of adsorption-desorption of N _ 2 by scanning electron microscope (SEM). The composition, structure and morphology of three kinds of supported organic chiral catalysts were characterized by TEM and TEM. The asymmetric series addition reaction of propionic aldehyde and cinnamaldehyde was used as a template. The effects of different reaction temperature, solvent and catalyst dosage on the performance of Michael/Michael/aldol asymmetric series catalytic reaction were investigated. The optimum reaction conditions of Michael/Michael/aldol series catalytic reaction were screened out. The catalyst AM/ProTMS HNsN 4 / b had the best catalytic performance in Michael/Michael/aldol asymmetric series catalytic reaction. In the asymmetric series addition reaction of all kinds of derivatives, the yield is 32 ~ 60 / 80 / 93 / 7 / 20, enantioselectivity 鈮，

本文編號(hào)：1694310