CN111889135B - 一种负载手性膦酸中空介孔纳米微球的制备方法及其产品和应用 - Google Patents
一种负载手性膦酸中空介孔纳米微球的制备方法及其产品和应用 Download PDFInfo
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- CN111889135B CN111889135B CN202010814234.5A CN202010814234A CN111889135B CN 111889135 B CN111889135 B CN 111889135B CN 202010814234 A CN202010814234 A CN 202010814234A CN 111889135 B CN111889135 B CN 111889135B
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- phosphonic acid
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
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- Thermal Sciences (AREA)
Abstract
本发明涉及一种负载手性膦酸中空介孔纳米微球的制备方法及其产品和应用,属于功能材料制备技术领域。本发明通过将聚苯乙烯/丙烯酸内核(PS/AA)、孔模板剂十六烷基三甲基溴化铵(CTAB)、有机手性膦酸、以及偏铝酸钠之间的相互作用,再通过洗涤的方式将孔模板(CTAB)、内层模板(PS/AA)除去,最终将手性膦酸负载在中空介孔纳米微球上形成一种特有的核壳结构的产物,该制备方法简单,产量高,可以作为催化剂催化不对称aldol反应方面的应用,具有良好的催化效果和重复使用性能。
Description
技术领域
本发明属于功能材料制备技术领域,具体涉及一种负载手性膦酸中空介孔纳米微球的制备方法及其产品和应用。
背景技术
有机催化的迅速发展使其成为在有机合成重要的支柱之一,有机催化进一步的发展主要集中在新型催化剂的催化模式:从相对简单的起始原料,构建一些复杂的光学结构,负载催化剂往往更加被重视。从另一个角度来看,分离有机催化剂再利用,负载非均相有机催化剂常常优选相应的均相催化剂,这是公认的、常用的策略,例如:金鸡纳碱类伯胺通过共价键结合,形成各种无机或有机载体,再进行异相不对称催化。负载型有机催化剂的发展具备催化多功能性和可重复使用性,完全符合绿色化学的观点。
在多功能材料的发展方面,介孔空心球被认为是一种有前途的候选环保材料。由于优异的性能、良好的结构得到广泛的认可。
因此在负载金鸡纳碱有机催化剂的有机无机杂化纳米空心球的基础上,制备一种新型铝膦材料,通过有机磷酸催化剂与偏铝酸钠的简便,快速的沉淀反应,制备一种负载手性膦酸中空介孔纳米微球,在水相催化不对称aldol反应,具有优异的催化结果(产率为65-98%,D.R.反式/顺式=82:18~95:5、92-98%ee和良好的可重复使用性(10次)。
发明内容
有鉴于此,本发明的目的之一在于提供一种负载手性膦酸中空介孔纳米微球的制备方法;本发明的目的之二在于提供一种负载手性膦酸中空介孔纳米微球;本发明的目的之三在于提供一种负载手性膦酸中空介孔纳米微球作为催化剂催化不对称aldol反应方面的应用。
为达到上述目的,本发明提供如下技术方案:
1.一种负载手性膦酸中空介孔纳米微球的制备方法,所述制备方法包括如下步骤:
(1)将聚苯乙烯/丙烯酸内核(PS/AA)、十六烷基三甲基溴化铵(CTAB)和有机膦酸加入水中,加入偏铝酸钠(NaAlO2)水溶液,加热搅拌反应,反应结束后依次进行抽滤、洗涤以及真空干燥,得到黄色粉末即为负载手性膦酸的纳米微球;
(2)将步骤(1)中制备的负载手性膦酸的纳米微球进行洗涤除去聚苯乙烯/丙烯酸内核和十六烷基三甲基溴化铵,即可得到负载手性膦酸中空介孔纳米微球。
优选的,所述有机膦酸按照如下方法制备:
(1)在无水无氧条件下向偶氮二异丁腈中加入巯乙基乙基磷酸酯和9-胺基表辛可尼丁或9-胺基表奎宁的氯仿溶液,加热搅拌进行回流反应,反应结束后减压浓缩,将浓缩的反应残留物进行萃取、干燥以及真空脱溶处理,再经过柱层析纯化即可得到膦酸酯化合物;
(2)将步骤(1)制备的膦酸酯化合物溶于二氯甲烷后,加入三甲基溴硅烷,室温下搅拌反应6h,反应结束后加入甲醇继续搅拌反应6h,减压浓缩得土黄色粘稠物,继续加入体积比为1:1的甲醇和乙醚组成的混合溶剂混合均匀后减压浓缩,重复3次后得到出产品,经过柱层析纯化即可得到有机膦酸。
优选的,所述偶氮二异丁腈、巯乙基乙基磷酸酯和9-胺基表辛可尼丁的摩尔比为6.95:83.33:27.77;所述偶氮二异丁腈、巯乙基乙基磷酸酯和9-胺基表奎宁的摩尔比为6.95:83.33:27.77;
优选的,所述膦酸酯化合物和三甲基溴硅烷的摩尔比为2.20:22.02。
优选的,所述聚苯乙烯/丙烯酸内核、有机膦酸和偏铝酸钠的质量摩尔比为100:0.3~4:0.15~2,g:mol:mol;
所述聚苯乙烯/丙烯酸内核和十六烷基三甲基溴化铵的质量比为100:13.6;
所述偏铝酸钠(NaAlO2)水溶液的添加速度为3~5滴/min。
优选的,所述聚苯乙烯/丙烯酸内核按照如下方法制备:
(1)在抽真空通氩气的情况下向过硫酸钾中加入苯乙烯、丙烯酸和去离子水,升温搅拌进行反应;
(2)搅拌结束后加水稀释,搅拌离心后依次用去离子水和乙醇洗涤,真空干燥后研磨即可得到聚苯乙烯/丙烯酸内核。
优选的,所述过硫酸钾、苯乙烯、丙烯酸和去离子水的摩尔体积比为0.19:4.4:14.6:100,mol:mol:mol:L。
优选的,所述升温搅拌具体为升温至80℃下以800rpm的转速搅拌24h。
优选的,所述加水稀释过程中升温搅拌进行反应后的溶液与水的体积比为1:1.
优选的,所述搅拌离心具体为以11800rpm的转速搅拌离心8min。
优选的,所述真空干燥为在50℃下真空干燥12h。
优选的,步骤(1)中所述加热搅拌反应为加热至60℃下搅拌反应6h。
优选的,步骤(1)中所述洗涤具体为采用纯水洗涤;
步骤(2)中所述洗涤具体为采用的溶剂为体积比为1:3的醋酸和四氢呋喃混合溶液、N,N-二甲基甲酰胺或甲苯中的任意一种进行洗涤。
2.根据上述制备方法制备得到的负载手性膦酸中空介孔纳米微球。
3.上述负载手性膦酸中空介孔纳米微球在催化不对称aldol反应中的应用。
优选的,所述应用具体为所述负载手性膦酸中空介孔纳米微球催化芳香醛与酮进行不对称aldol反应。
本发明的有益效果在于:
1、本发明公开了一种负载手性膦酸中空介孔纳米微球的制备方法,首先通过将有机膦酸、聚苯乙烯/丙烯酸内核以及偏铝酸钠之间的相互作用,再通过洗涤的方式将内层模板(聚苯乙烯/丙烯酸内核PS/AA)和孔模板(十六烷基三甲基溴化铵CTAB)除去,最终将手性膦酸负载在中空介孔纳米微球上形成一种特有的核壳结构的产物,该制备方法简单,产量高。
2、本发明还公开了本发明制备的负载手性膦酸中空介孔纳米微球作为催化剂催化不对称aldol反应方面的应用,由于上述纳米微球催化剂兼有手性伯胺、酸两种特性,对不对称aldol反应具有良好的催化效果(催化aldol反应的产率为65~98%,其中反式和顺式的比例为82:18~95:5、ee为92~98%),并且容易回收、能够重复使用(10次)。
本发明的其他优点、目标和特征在某种程度上将在随后的说明书中进行阐述,并且在某种程度上,基于对下文的考察研究对本领域技术人员而言将是显而易见的,或者可以从本发明的实践中得到教导。本发明的目标和其他优点可以通过下面的说明书来实现和获得。
附图说明
为了使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明作优选的详细描述,其中:
图1为实施例1制备的聚苯乙烯/丙烯酸内核(PS/AA)的SEM图;
图2为实施例2中制备的有机膦酸铝空心壳结构的SEM图;
图3为实施例2中制备的有机膦酸铝空心壳结构的TEM图;
图4为负载手性膦酸中空介孔纳米微球的制备流程;
图5为实施例2~5中制备的产物的孔径测试结果,其中a、b、c和d分别为实施例2、实施例3、实施例4和实施例5中制备的纳米微球;
图6为实施例2~5中制备的产物的红外光谱测试结果,其中a、b、c和d分别为实施例2、实施例3、实施例4和实施例5中制备的纳米微球;
图7为实施例2~5中制备的产物的SEM测试结果,其中a、b、c和d分别为实施例2、实施例3、实施例4和实施例5中制备的纳米微球;
图8为实施例2中制备的产物催化不对称aldol反应后的高效液相色谱图;
图9为本发明制备的负载手性膦酸中空介孔纳米微球作为催化剂催化不对称aldol反应的机理图。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。需要说明的是,在不冲突的情况下,以下实施例及实施例中的特征可以相互组合。
下列实施例中涉及到的CDPC/n2、CDPC/n4、CDPC/n6以及QNPC/n4结构式如下所示:
其中CDPC/n2中n=2、R为氢;CDPC/n4中n=4、R为氢;CDPC/n6中n=6、R为氢;QNPC/n4中n=4、R为甲氧基;
实施例1
制备聚苯乙烯/丙烯酸内核PS/AA,具体制备方法如下:
(1)先100mL的双颈瓶中加入过硫酸钾(0.05g,0.19mmol,0.2mol%),抽真空通氩气并置换三次,加入苯乙烯(5mL,4.4mmol)、丙烯酸(1.0mL,14.6mmol)和预超声的去离子水(100mL),将温度升至80℃后以800rpm的转速搅拌24h后停止反应得到母液;
(2)将母液置于离心管中,加等体积的水稀释,以11800rpm的转速离心8min,然后依次用与母液等体积的去离子水和乙醇分别洗涤2次,从而从母液中离心分离出产品,在50℃下真空干燥12h,将干燥后的产物充分研磨得平均粒径约325±11nm的聚苯乙烯微球(PS/AA),即可作为后续制备负载手性杂多酸中空介孔纳米微球中的聚苯乙烯/丙烯酸内核。
实施例2
制备负载手性膦酸中空介孔纳米微球,具体的制备步骤如下:
1、制备膦酸酯化合物
将6.95mmol(1.14g)偶氮二异丁腈(AIBN)加入250mL的三颈瓶中,抽真空后通入氮气置换,氮气置换三次形成无水无氧条件;
用注射器加入83.33mmol(21.5g)碳链为2的巯乙基乙基磷酸酯(结构通式为通式I,其中n=2)和27.77mmol(8.15g)9-胺基表辛可尼丁的100mL氯仿溶液;
混合物在85℃条件下搅拌回流48h,反应结束后进行减压浓缩得到反应残留物,将其转移至500mL分液漏斗中,用15%的稀盐酸溶液调至pH=1后用50mL三氯甲烷萃取4次,除去有机相,继续加入氨水调节至pH=10,用50mL三氯甲烷萃取4次,合并有机相,用无水Na2SO4干燥后真空脱溶,得棕淡黄色油状粘稠的出产品;
粗产品经柱层析纯化(氯仿/甲醇=50:1→40:1→20:1→4:1),得黄棕色油状粘稠物即为CDPE/n2(9.6g,62.1%)。
2、制备有机膦酸
将2.20mmol(1.21g)制备的CDPE/n2加入装有磁力搅拌装置的50mL单颈瓶中,加入15mL二氯甲烷,搅拌均匀后,缓慢滴加三甲基溴硅烷22.02mmol(2.92mL),室温搅拌8h;
反应结束后减压浓缩至干,向单颈瓶中加入12mL甲醇,继续搅拌6h,减压浓缩,得土黄色粘稠物;
继续加入24mL甲醇和乙醚(v/v=1:1)的混合溶剂,减压浓缩,重复3次,得黄色固体粗产物;
粗产品经柱层析纯化(氯仿/甲醇=50:1→20:1→1:1),得淡黄色固体CDPC/n2(0.92g,90%)即为空心壳结构的有机膦酸。
3、制备负载手性膦酸核壳纳米微球
将上述制备的有机膦酸在装有磁力搅拌装置的250mL单颈瓶中,分别加入聚苯乙烯/丙烯酸内核PS/AA(100mg)、十六烷基三甲基溴化铵CTAB(13.6mg)、CDPC/n2(150mg,0.3mmol)和1.0mL水,微量进样器以3~5滴/min的速度滴加50.0mL NaAlO2(12.3mg,0.15mmol)水溶液;
添加完毕后将单颈瓶升温至60℃并保温继续搅拌6h,抽滤,15ml的纯水洗涤4次,真空干燥,得黄色粉末状负载手性膦酸核壳纳米微球(212mg,73%)。
4、制备负载手性膦酸中空介孔纳米微球
将上述制备得到的负载手性膦酸纳米微球用50mL体积比为1:3醋酸和四氢呋喃形成的混合溶剂洗涤4次(或者用50mL N,N-二甲基甲酰胺洗涤3次或者用50mL甲苯洗涤6次),除去内层模板(聚苯乙烯/丙烯酸内核PS/AA)和孔模板(十六烷基三甲基溴化铵CTAB),即可获得负载手性膦酸中空介孔纳米微球AlP@CDPC/n2。
实施例3
同样按照实施例2中的流程和方法,只是将实施例2中添加的聚苯乙烯/丙烯酸内核PS/AA、有机膦酸和偏铝酸钠的质量摩尔比调整为50:2:1,g:mol:mol。
实施例4
同样按照实施例2中的流程和方法,只是将实施例2中添加的聚苯乙烯/丙烯酸内核PS/AA、有机膦酸和偏铝酸钠的质量摩尔比调整为75:2:1,g:mol:mol。
实施例5
同样按照实施例2中的流程和方法,只将实施例2中添加的聚苯乙烯/丙烯酸内核PS/AA、有机膦酸和偏铝酸钠的质量摩尔比调整为200:2:1,g:mol:mol。
本发明采用的实施例1中制备的聚苯乙烯/丙烯酸内核(PS/AA)的SEM图如图1所示,图2和图3分别为本发明实施例2中制备的有机膦酸铝空心壳结构的SEM和TEM图,本发明制备负载手性膦酸中空介孔纳米微球的流程如图4所示,将实施例2~5中制备的负载手性膦酸中空介孔纳米微球进行孔径测试,其结果如图5所示,其中a、b、c和d分别为实施例2、实施例3、实施例4和实施例5中制备的纳米微球的孔径分布;将实施例2~5中制备的负载手性膦酸中空介孔纳米微球进行红外光谱测试,其结果如图6所示,其中a、b、c和d分别为实施例2、实施例3、实施例4和实施例5中制备的纳米微球的红外光谱图,制备的纳米微球都具有膦酸官能团的吸收峰;将实施例2~5中制备的负载手性膦酸中空介孔纳米微球进行SEM测试,其结果如图7所示,其中a、b、c和d分别为实施例2、实施例3、实施例4和实施例5中制备的纳米微球的SEM图。
从图2~4中的测试结果可以看出,在制备过程中通过调整聚苯乙烯/丙烯酸内核(PS/AA)、有机膦酸和偏铝酸钠的质量摩尔比(100:0.3~4:0.15~2,g:mol:mol)均能够得到负载手性膦酸中空介孔纳米微球,只是不同的质量摩尔比导致纳米微球的成分比例、孔径以及厚度不同。
实施例6
按照实施例2中的制备流程,将实施例2中的通式为I、n=2的巯乙基乙基磷酸酯替换成通式为I、n=4或n=6,分别制备得到AlP@CDPC/n4(135mg,79%)、AlP@CDPC/n6(115mg,63%),同样如实施例2~5中将聚苯乙烯、有机膦酸和偏铝酸钠的质量摩尔比在100:0.3~4:0.15~2,g:mol:mol的范围内变动也可以制备得到孔径以及厚度不同的AlP@CDPC/n4和AlP@CDPC/n6。
将实施例2中的9-胺基表辛可尼丁替换为9-胺基表奎宁制备得到AlP@QNPC/n2(139mg,83%),同样如实施例2~3中将、有机膦酸和偏铝酸钠的质量摩尔比在100:0.3~4:0.15~2,g:mol:mol的范围内变动也可以制备得到孔径以及厚度不同AlP@QNPC/n2。
实施例7
将实施例2中制备得到的产物AlP@CDPC/n2作为催化剂用于催化不对称aldol反应,以催化环己酮和对硝基苯甲醛的不对称aldol反应为例,其催化反应的反应式式如下:
具体催化反应过程如下:
向试管中加入负载手性膦酸中空介孔纳米微球AlP@CDPC/n2(9.92mg)、环己酮(0.383g,4.83mmol)和H2O(1mL),将反应混合物置于封闭体系中搅拌15min,加入对硝基苯甲醛(37.75mg,0.25mmol)。反应混合物在20℃搅拌72h(TLC监测),加入乙酸乙酯(3mL)萃取有机相,离心分离催化剂。分离的有机相用无水硫酸钠干燥、过滤和真空脱溶。粗产品经硅胶柱层析纯化【石油醚/乙酸乙酯(v/v=10/1→2/1)为流动相】,旋转蒸发除去溶剂,称重计算产率,HPLC测定(结果如图8所示)对映选择性中ee构型的百分含量为96%,1H NMR确定非对映选择性(92/8Dr)。
由于实施例3~5中制备的负载手性膦酸中空介孔纳米微球相比于实施例2的产品只是在纳米微球的成分比例、孔径以及厚度方面存在差异,因此将实施例3~5中制备的负载手性膦酸中空介孔纳米微球同样用于催化上述环己酮和对硝基苯甲醛的不对称aldol反应,其催化结构与实施例2的纳米微球的催化结果显示。
同样的用实施例6中按照实施例2的方法和比例制备得到的AlP@CDPC/n4(yield=85%、97%ee、93/7Dr)、AlP@CDPC/n6(yield=79%、95%ee、90/10Dr)以及AlP@QNPC/n4(yield=91%、98%ee、95/5Dr)对上述反应进行催化,也同样能够得到如AlP@CDPC/n2相近的催化效果。
另外将反应物中的4-硝基苯甲醛分别更换为3-硝基苯甲醛、2-硝基苯甲醛、4-甲基苯甲醛、3-甲基苯甲醛、2-甲基苯甲醛,采用上述制备的负载手性膦酸中空介孔纳米微球作为催化剂,分别得到不同选择性催化底物。
综上所述,本发明公开的制备方法制备的负载手性膦酸中空介孔纳米微球能够用于催化不对称aldol反应,其原因如下:不对称aldol反应是在手性伯胺催化剂和酸催化剂(如三氟磺酸等)的协同催化作用下完成的,首先手性伯胺催化剂与环己酮形成烯胺中间体,质子化的叔胺通过氢键活化芳香醛,在手性催化剂的空间控制下,通过烯胺对活化羰基的亲核加成,立体选择性生成β-羟基酮,而本发明制备的纳米微球兼有手性伯胺、酸两种特性,作为催化剂的催化机理如图9所示,对不对称aldol反应具有良好的催化效果(催化aldol反应的产率为65~98%,其中反式和顺式的比例为82:18~95:5、ee为92~98%),并且容易回收、能够重复使用(10次)。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (5)
1.一种负载手性膦酸中空介孔纳米微球的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)将聚苯乙烯/丙烯酸内核、十六烷基三甲基溴化铵和有机膦酸加入水中,加入偏铝酸钠水溶液,加热搅拌反应,反应结束后依次进行抽滤、洗涤以及真空干燥,得到黄色粉末即为负载手性膦酸的纳米微球;
(2)将步骤(1)中制备的负载手性膦酸的纳米微球进行洗涤除去聚苯乙烯/丙烯酸内核和十六烷基三甲基溴化铵,即得到负载手性膦酸中空介孔纳米微球;
步骤(1)中所述聚苯乙烯/丙烯酸内核、有机膦酸和偏铝酸钠的质量摩尔比为100g:(0.3~4)mol:(0.15~2)mol,所述聚苯乙烯/丙烯酸内核和十六烷基三甲基溴化铵的质量比为100:13.6,所述偏铝酸钠水溶液的添加速度为3~5滴/min;
所述聚苯乙烯/丙烯酸内核按照如下方法制备:
A、在抽真空通氩气的情况下向过硫酸钾中加入苯乙烯、丙烯酸和去离子水,升温搅拌进行反应;
B、搅拌结束后加水稀释,搅拌离心后依次用去离子水和乙醇洗涤,真空干燥后研磨即得到聚苯乙烯/丙烯酸内核。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中所述洗涤具体为采用纯水洗涤,步骤(1)中所述加热搅拌反应为加热至60℃下搅拌反应6h;
步骤(2)中所述洗涤具体为采用体积比为1:3的醋酸和四氢呋喃混合溶液、N,N-二甲基甲酰胺或甲苯中的任意一种溶剂进行洗涤。
3.根据权利要求1~2任一项所述的制备方法制备得到的负载手性膦酸中空介孔纳米微球。
4.权利要求3所述负载手性膦酸中空介孔纳米微球在催化不对称aldol反应中的应用。
5.根据权利要求4所述的应用,其特征在于,所述应用具体为所述负载手性膦酸中空介孔纳米微球催化芳香醛与酮进行不对称aldol反应。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102688779A (zh) * | 2012-06-08 | 2012-09-26 | 凯莱英医药集团(天津)股份有限公司 | 一种膦配体钌催化剂的制备及其在不对称还原中的应用 |
CN107970878A (zh) * | 2017-11-09 | 2018-05-01 | 南华大学 | 一种磷酸基团官能化中空介孔二氧化硅微球的制备方法 |
CN108682814A (zh) * | 2018-05-11 | 2018-10-19 | 上海应用技术大学 | 一种片状磷酸铁锂/碳复合材料的制备方法 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102688779A (zh) * | 2012-06-08 | 2012-09-26 | 凯莱英医药集团(天津)股份有限公司 | 一种膦配体钌催化剂的制备及其在不对称还原中的应用 |
CN107970878A (zh) * | 2017-11-09 | 2018-05-01 | 南华大学 | 一种磷酸基团官能化中空介孔二氧化硅微球的制备方法 |
CN108682814A (zh) * | 2018-05-11 | 2018-10-19 | 上海应用技术大学 | 一种片状磷酸铁锂/碳复合材料的制备方法 |
Non-Patent Citations (3)
Title |
---|
Asymmetric Direct Aldol Reactions Catalyzed by a Simple Chiral Primary Diamine-Bronsted Acid Catalyst in/on Water;Li, L,et al.;《SYNTHETIC COMMUNICATIONS》;20090129;第764-774页 * |
有机膦酸铝负载多功能有机手性催化剂的制备及其在不对称 aldol 反应中的应用;谢广新;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20170215;第15-46页 * |
空心介孔有机聚合物纳米球负载手性多催化剂的构筑及多催化剂间相互作用机制研究;谢广新;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20200115;第17-21,46-59页 * |
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