CN113244951A - 介孔分子筛负载的催化剂及其应用 - Google Patents

介孔分子筛负载的催化剂及其应用 Download PDF

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CN113244951A
CN113244951A CN202110206143.8A CN202110206143A CN113244951A CN 113244951 A CN113244951 A CN 113244951A CN 202110206143 A CN202110206143 A CN 202110206143A CN 113244951 A CN113244951 A CN 113244951A
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赵丹丹
张羽杰
付译瑶
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Tianjin University of Commerce
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Abstract

本发明公开了一种介孔分子筛MCM‑41负载的手性冠醚催化剂及其应用。本发明的催化剂，其结构如式(I)所示。所述催化剂式(I)可高对映选择性制备非天然氨基酸，催化剂催化对映选择性高，分离纯化简单，可反复循环利用。

Description

介孔分子筛负载的催化剂及其应用
技术领域
本发明涉及催化材料领域，具体地说，涉及一种介孔分子筛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
本发明提供的MCM-41负载的手性冠醚催化剂，结构如式(I)所示：
Figure BDA0002950740220000011
R2与R3连接形成的a环为苯环或环己烷。
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
Figure BDA0002950740220000012
中，R1为基叔丁基、环己基；式VII可由α-氨基砜与KCN合成制得，如反应式为：
Figure BDA0002950740220000021
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-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)与氯丙基化的介孔分子筛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：
Figure BDA0002950740220000022
其中R为苯基或环己基，即，步骤b中的N-Boc-二胺化合物分别用N-Boc-邻苯二胺、N-Boc-1，2-环己二胺时，对应的催化剂产物依次为式Ia、Ib,Ia、Ib的所述a环依次为苯环或环己烷。
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中的碱可独立选自：Cs2CO3,K2CO3,Na2CO3。
本发明的有益效果主要体现在：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≥98％。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
中间体(V)的制备：
氮气氛围下，将中间体(IV)(1.0mmol)加入50mL乙腈，加入碳酸铯(1.2mmol)，加热回流，再并列加入不同的N-Boc-二胺各1.1mmol(a、N-Boc-邻苯二胺；b、N-Boc-1，2-环己二胺)，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)，制得各自的中间体(V)。
使用N-Boc-邻苯二胺制得的中间体(Va)为
Figure BDA0002950740220000041
其收率86％。ESI-MS(m/z):905[M+H]+；1H NMR(300MHz，CDCl3)δ8.54(s,1H),8.01(s,1H),7.79(t,J＝8.9Hz,2H),7.77(d,J＝8.2Hz,1H),7.43(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.18-7.08(m,2H),6.58-6.42(m,4H),4.95(s,1H),4.21(m,2H),3.97-3.71(m,8H),3.30-3.24(m,2H),3.21(t,J＝4.5Hz,2H),2.57(s,3H),1.43(s,9H)。
中间体(Vb)
Figure BDA0002950740220000051
收率91％。ESI-MS(m/z):911[M+H]+；1H NMR(300MHz，CDCl3)δ8.52(s,1H),8.00(s,1H),7.78(t,J＝8.9Hz,2H),7.76(d,J＝8.2Hz,1H),7.42(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.18-7.07(m,2H),4.22(m,2H),3.97-3.71(m,9H),3.22(t,J＝4.5Hz,2H),3.19(m,1H),2.83-2.72(m,2H),2.57(s,3H),2.01(s,1H),1.78-1.49(m,5H),1.40(s,9H),1.39(m,3H)。
实施例4
中间体(VI)的制备：
氮气氛围下，并列将不同的中间体V(上一实施例制得的Va、Vb)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，制得各自的中间体(VI)。用Va制得的中间体VIa
Figure BDA0002950740220000052
其收率为90％，1H NMRδ：8.53(s,1H),8.00(s,1H),7.78(t,J＝8.9Hz,2H),7.76(d,J＝8.1Hz,1H),7.43(t,J＝7.3Hz,2H),7.33-7.27(m,2H),7.18-7.08(m,2H),6.57-6.41(m,4H),5.01(s,1H),4.21-4.15(m,2H),3.95-3.70(m,8H),3.57(s,2H),3.22(t,J＝4.8Hz,2H)。
中间体VIb
Figure BDA0002950740220000061
收率为95％，1HNMRδ：8.52(s,1H),8.00(s,1H),7.78(t,J＝8.9Hz,2H),7.76(d,J＝8.2Hz,1H),7.42(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.17-7.07(m,2H),4.95(s,1H),4.19-4.15(m,2H),3.96-3.70(m,9H),3.21(t,J＝4.5Hz,2H),3.19-3.10(m,1H),2.04(s,2H),1.78-1.49(m,5H),1.39-1.21(m,3H)。
实施例5
催化剂式(I)的制备：
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，再并列加入中间体(VI)(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(Ia)负载量为0.95mmol/g,催化剂式(Ib)负载量为0.93mmol/g。
实施例6
N2保护下，将N-Boc-1-苯磺酰基-2，2-二甲基丙胺(1.0mmol)与KCN(1.1mmol)加入到干燥的15mL甲苯中，冷却至0℃，加入107mg式(Ia)，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，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)-叔丁基甘氨酸盐酸盐，收率87％，97％ee。1H NMR(300MHz,D2O):δ3.83(s,1H),1.10(s,9H)；ee用HPLC[手性OA-5000柱,250x4.6mm；流动相：2mmol/LCuSO4溶液/乙腈＝90:10；流速:1.0mL/min；254nm]测定，tR＝17.3min(major),tS＝14.5min。
实施例7
N2保护下，将N-Boc-1-苯磺酰基-1-环己基甲胺(1.0mmol)与KCN(1.1mmol)加入到干燥的15mL甲苯中，冷却至0℃，加入113mg式(Ib)，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，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)-环己基甘氨酸盐酸盐，收率76％，96％ee。1H NMR(300MHz,D2O):δ3.91(d,J＝4.5Hz,1H),2.00(m.1H),1.77(s,3H),1.66-1.64(m,2H),1.35-1.26(m,5H)；ee用HPLC[手性OA-5000柱,250x4.6mm；流动相：2mmol/L CuSO4溶液/乙腈＝90:10；流速:1.0mL/min；254nm]测定，tR＝53.3min(major),tS＝47.2min。
实施例8
以N-Boc-1-苯磺酰基-2，2-二甲基丙胺与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。
表1催化剂式(Ia)的循环利用次数
Figure BDA0002950740220000081

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：
Figure FDA0002950740210000011
R2与R3连接形成的a环为苯环或环己烷。
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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WO2022179557A1 (zh) * 2021-02-24 2022-09-01 周学明 催化剂及其应用
CN117358291A (zh) * 2023-12-08 2024-01-09 山东新和成药业有限公司 一种用于制备氧杂双环十六烯的催化剂及其制备方法和应用
CN117358291B (zh) * 2023-12-08 2024-02-27 山东新和成药业有限公司 一种用于制备氧杂双环十六烯的催化剂及其制备方法和应用

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