CN112973789B - 新介孔材料负载的催化剂及其应用 - Google Patents
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
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Abstract
本发明涉及催化材料领域，具体公开了一种新介孔材料负载的催化剂及其应用。本发明的催化材料，其结构如式(I)所示。所述催化材料式(I)可高对映选择性制备非天然氨基酸，催化对映选择性高，分离纯化简单，可反复循环利用。
Description
技术领域
本发明涉及催化材料领域，具体地说，涉及一种新介孔材料负载的催化剂及其应用。
背景技术
手性冠醚催化剂是一种均相催化剂，存在不易从反应体系分离，难以回收利用的缺点，手性冠醚催化剂价格昂贵，应用成本高。
MCM-41分子筛是介孔分子筛中最典型的一种。作为一种介孔分子筛，MCM-41的孔道为有序六边形结构，其孔径可以在2-10nm之间调控，并且具有极高的比表面积(高达1500m2/g)、孔体积(1.3ml/g)以及优良的热稳定性。
发明内容
本发明的目的在于提供一种新的介孔材料负载的手性冠醚催化剂及其制备方法与应用。
本发明提供的一种MCM-41负载的手性冠醚催化剂，结构如式(I)所示：
本发明还提供了所述式(I)催化剂在催化合成非天然氨基酸中的应用，如为式VII的(R)-氨基酸
式VII中，R1为苯基、3-氯苯基；式VII可由α-氨基砜与KCN合成制得，如反应式为：
本发明所述MCM-41负载的手性冠醚催化剂的制备方法可包括以下步骤：
a.N2保护下，(R)-BINOL衍生物(II)与三乙二醇醚对甲苯磺酸酯(III)在碱存在下缩合制得中间体(IV)；
b.N2保护下，在碱作用下，中间体(IV)与N-Boc-1，2-二苯基乙二胺缩合，制得中间体(V)；
c.N2保护下，中间体(V)在HCl作用下脱保护，制得中间体(VI)；
d.N2保护下，中间体(VI)与介孔分子筛MCM-41-Cl在KI与碱存在下缩合制得MCM-41负载的手性冠醚催化剂式(I)；
其具体合成路线可如下所示：
在上述MCM-41负载的手性冠醚催化剂的制备方法中，所述的步骤a，b和d中的碱独立选自：Cs2CO3,K2CO3,Na2CO3。
本发明的有益效果主要体现在：涉及的MCM-41负载的手性冠醚催化剂为全新的催化剂，所述的催化剂式(I)简单过滤即可以与反应液分离，式(I)回收率≥97％。回收的催化剂式(I)能循环利用，循环使用10次，催化活性不变。催化剂的合成路线简单，收率高，可以催化多种底物的α-氨基砜与KCN不对称反应，制备的非天然氨基酸光学纯度高。
具体实施方式
实施例1
氮气氛围下，将1g介孔分子筛MCM-41于50℃真空干燥过夜。加入30mL二甲苯与4mL3-氯丙基三甲氧基硅烷，室温下超声处理10min，加热回流24h,冷至rt,离心，异丙醇洗涤，50℃真空干燥12h，制得氯丙基化MCM-41(MCM-41-Cl)。
实施例2
取(R)-BINOL衍生物(II)(582mg,1.0mmol)于反应瓶中，置换氮气后加入50mL乙腈，加入研磨过的碳酸钾粉末(166mg,1.2mmol)，加热回流，将三乙二醇醚对甲苯磺酸酯(III)(503mg,1.1mmol)溶于10mL乙腈中，注射加入反应体系。TLC监测，保温反应8小时，减压蒸出乙腈，加水，二氯甲烷萃取，干燥后，硅胶柱层析分离纯化(PE/EA＝4:1)，制得中间体(IV)，收率90％。ESI-MS(m/z):868[M]+；1H NMR(300MHz，CDCl3)δ8.49(s,1H),7.82(d,J＝7.2Hz,2H),7.78(d,J＝8.2Hz,1H),7.73(d,J＝6.9Hz,2H),7.40(m,3H),7.33-7.23(m,3H),7.06(d,J＝8.8Hz,2H),3.97-3.71(m,4H),3.29-3.24(m,8H),3.21(t,J＝4.5Hz,2H),2.57(s,3H),2.43(s,3H)。
实施例3
氮气氛围下，将中间体(IV)(869mg,1.0mmol)加入50mL乙腈，加入碳酸铯(391mg,1.2mmol)，加热回流，再加入N-Boc-1，2-二苯基乙二胺(343mg,1.1mmol)，反应36h，减压蒸出乙腈，加水，二氯甲烷萃取，干燥后，硅胶柱层析分离纯化(PE/EA＝4:1)，制得中间体(V)，收率89％。ESI-MS(m/z):1009[M+H]+；1H NMR(300MHz，CDCl3)δ8.54(s,1H),8.02(s,1H),7.79(t,J＝8.9Hz,2H),7.77(d,J＝8.2Hz,1H),7.42(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.21-7.07(m,12H),5.51(m,1H),4.93(m,1H),4.21(m,2H),3.97-3.71(m,8H),3.21(t,J＝4.5Hz,2H),2.82-2.71(m,2H),2.57(s,3H),2.03(s,1H),1.41(s,9H)。
实施例4
氮气氛围下，将中间体V(1010mg,1.0mmol)加入到4mL甲醇与12mL二氯甲烷中，加入50mL浓盐酸，室温搅拌24h，加入碳酸氢钠饱和溶液，搅拌，用二氯甲烷萃取，水洗，无水硫酸钠干燥，过滤，减压蒸干，制得中间体(VI),收率92％。ESI-MS(m/z):865[M+H]+；1H NMRδ：8.54(s,1H),7.79(t,J＝8.9Hz,2H),7.77(d,J＝8.2Hz,1H),7.42(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.21-7.07(m,12H),5.53(m,2H),5.02(s,1H),4.21(m,2H),3.97-3.71(m,8H),2.73(m,2H),2.03(s,3H)。
实施例5
氮气氛围下，将1g MCM-41-Cl加入到50mL乙腈中，加入碳酸钠(1.2mmol)和KI(1.2mmol)，剧烈搅拌，再加入中间体(VI)(1.75g,2.0mmol)的20mL乙腈溶液，加热回流48h，冷却，过滤，水洗，制得MCM-41负载的手性冠醚催化剂式(I)。催化剂式(I)负载量为0.90mmol/g。
实施例6
N2保护下，将N-Boc-1-苯磺酰基-1-苯基甲胺(1.0mmol)与KCN(1.1mmol)加入到干燥的15mL甲苯中，冷却至0℃，加入107mg式(I)，反应60h，过滤，滤饼用水打浆，过滤，重复3次，最后用甲醇洗涤2次，真空干燥，回收式(I)，循环利用。滤液中加入6NHCl，回流反应3h，冷至室温，分层，水相加热回流3h，冷至室温，乙酸乙酯洗涤，减压浓缩至干，异丙醇重结晶，制得(R)-苯甘氨酸盐酸盐，收率81％，99％ee。1H NMR(300MHz,D2O):δ7.53(m,5H),5.25(s,1H)；ee用HPLC[手性OA-5000柱,250x4.6mm；流动相：2mmol/L CuSO4溶液/异丙醇＝95:5；流速:1.0mL/min；254nm]测定，tR＝19.8min(major),tS＝13.0min。
实施例7
N2保护下，将N-Boc-1-苯磺酰基-1-(3-氯苯基)甲胺(1.0mmol)与KCN(1.1mmol)加入到干燥的15mL甲苯中，冷却至0℃，加入107mg式(I)，反应60h，过滤，滤液中加入6NHCl，回流反应3h，冷至室温，分层，有机相回收甲苯，水相加热回流3h，冷至室温，乙酸乙酯洗涤，减压浓缩至干，异丙醇重结晶，制得(R)-3-氯苯甘氨酸盐酸盐，收率72％，ee值96％。1H NMR(300MHz,D2O):δ6.95(m,1H),7.08(m,3H)4.81(s,1H)；ee用HPLC[手性OA-5000柱,250x4.6mm；流动相：2mmol/L CuSO4溶液/乙腈＝93:7；流速:0.8mL/min；254nm]测定，tR＝19.7min(major),tS＝15.9min。
实施例8
以N-Boc-1-苯磺酰基-1-苯基甲胺与KCN反应为模板，按实施例6操作，考察催化剂式(I)的循环利用次数。结果显示，催化剂循环使用10次，催化活性不变，具体如下表：
Claims (2)
1.介孔材料MCM-41负载的手性冠醚催化剂，其结构如式(I)所示：
2.根据权利要求1所述的介孔材料MCM-41负载的手性冠醚催化剂在催化合成非天然氨基酸中的应用。
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