WO2022179557A1 - 催化剂及其应用 - Google Patents

催化剂及其应用 Download PDF

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WO2022179557A1
WO2022179557A1 PCT/CN2022/077644 CN2022077644W WO2022179557A1 WO 2022179557 A1 WO2022179557 A1 WO 2022179557A1 CN 2022077644 W CN2022077644 W CN 2022077644W WO 2022179557 A1 WO2022179557 A1 WO 2022179557A1
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catalyst
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周学明
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周学明
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Priority to CN202280016541.6A priority Critical patent/CN116887917A/zh
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Priority to ZA2024/00088A priority patent/ZA202400088B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • 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
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the chiral crown ether catalyst is not easy to recycle, and the cost is high.
  • MCM-41 As a mesoporous molecular sieve, MCM-41 has extremely high specific surface area, pore volume and excellent thermal stability.
  • the invention provides a chiral crown ether catalyst, the structure of which is shown in formula (VI):
  • Both R2 and R3 are phenyl groups, or R2 and R3 are connected to form an A ring, and the A ring is a benzene ring or a cyclohexane.
  • the present invention also provides a mesoporous material of MCM-41 supported catalyst VI, the structure of which is shown in formula (I):
  • the present invention also provides the application of the catalytic material of formula (I) in the catalytic synthesis of unnatural amino acids, such as (R)-amino acids of formula VII Among them, R1 is phenyl, 3-chlorophenyl, tert-butyl, cyclohexyl; Formula VII can be synthesized by ⁇ -aminosulfone and KCN, and the reaction formula is:
  • the preparation method of formula (I) of the present invention may comprise:
  • intermediate (IV) is condensed with N-Boc-diamine to obtain intermediate (V);
  • intermediate (VI) is condensed with chloropropylated mesoporous molecular sieve MCM-41-Cl in the presence of KI and alkali to obtain formula (I);
  • R is phenyl, cyclohexyl or 1,2-diphenylethyl, that is, the N-Boc-diamine compound in step b is respectively N-Boc-o-phenylenediamine, N-Boc-1,2 -In the case of cyclohexanediamine and N-Boc-1,2-diphenylethylenediamine, the corresponding catalytic materials obtained are successively formulas Ia, Ib, Ic, and the A rings of Ia and Ib are successively benzene rings or Cyclohexane, the described R of Ic and R are phenyl, and the preparation of Ic can be as follows:
  • the bases in the steps a, b and d are independently selected from: Cs 2 CO 3 , K 2 CO 3 , Na 2 CO 3 .
  • the preparation of MCM-41-Cl of the present invention can be as follows:
  • the catalyst material formula (I) of the present invention can be separated by simple filtration, and the recovery rate of formula (I) is ⁇ 97%.
  • the recovered formula (I) can be recycled for 10 times, and the catalytic activity remains unchanged.
  • intermediate (IV) (1.0 mmol) was added to 50 mL of acetonitrile, cesium carbonate (1.2 mmol) was added, heated to reflux, and 1.1 mmol of different N-Boc-diamines were added in parallel to carry out a parallel condensation reaction (each The diamines of each reaction are: a, N-Boc-o-phenylenediamine; b, N-Boc-1,2-cyclohexanediamine; c, N-Boc-1,2-diphenylethylenediamine ), reacted for 36h, evaporated acetonitrile under reduced pressure, added water, extracted with dichloromethane, dried, separated and purified by silica gel column chromatography to obtain the respective intermediate (V).
  • MCM-41-Cl Under nitrogen atmosphere, 1 g of MCM-41-Cl was added to 50 mL of acetonitrile, sodium carbonate (1.2 mmol) and KI (1.2 mmol) were added, vigorously stirred, and 3 intermediates (VI) of Example 3 were added in parallel (2.0 mmol) in 20 mL of acetonitrile, heated to reflux for 48 h, cooled, filtered, and washed with water to prepare MCM-41-supported catalytic material formula (I).
  • the loading amount of the catalyst formula (Ia) is 0.95 mmol/g
  • the loading amount of the catalyst formula (Ib) is 0.93 mmol/g.
  • the loading amount of the catalyst formula (I) is 0.90 mmol/g.
  • N-Boc-1-benzenesulfonyl-2,2-dimethylpropylamine 1.0 mmol
  • KCN 1.1 mmol
  • the filter cake was slurried with water, filtered, repeated 3 times, washed 2 times with methanol at last, vacuum-dried, recovered formula (I), and recycled.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

一种手性冠醚催化剂及其应用。所述催化剂结构如式(VI)所示，其中R2与R3均为苯基，或者R2与R3连接形成A环，A环为苯环或环己烷；催化剂(VI)的负载式材料可用于催化合成非天然氨基酸，所述材料通过简单过滤即可分离，实现循环利用。

Description

催化剂及其应用 背景技术
手性冠醚催化剂不易回收利用，成本高。
作为一种介孔分子筛，MCM-41有极高的比表面积、孔体积以及优良的热稳定性。
发明内容
本发明提供了手性冠醚催化剂，其结构如式(VI)所示：
Figure PCTCN2022077644-appb-000001
R2与R3均为苯基，或者R2与R3连接形成A环，A环为苯环或环己烷。
本发明还提供了MCM-41负载催化剂VI的介孔材料，结构如式(I)所示：
Figure PCTCN2022077644-appb-000002
本发明还提供了所述式(I)催化材料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 PCTCN2022077644-appb-000003
中，R1为苯基、3-氯苯基、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 PCTCN2022077644-appb-000004
本发明所述式(I)的制备方法可包括：
a.N 2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.N 2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.N 2保护下，中间体(V)在HCl作用下脱保护，制得中间体(VI)；
d.N 2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式(I)；
其具体合成路线可如下所示：
Figure PCTCN2022077644-appb-000005
其中R为苯基、环己基或1，2-二苯基乙基，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、N-Boc-1，2-二苯基乙二胺时，对应制得的催化材料依次为式Ia、Ib、Ic,Ia、Ib 的所述A环依次为苯环或环己烷，Ic的所述R2与R3均为苯基，Ic的制备可如下：
Figure PCTCN2022077644-appb-000006
所述步骤a，b和d中的碱独立选自：Cs 2CO 3,K 2CO 3,Na 2CO 3。
本发明MCM-41-Cl的制备可如下：
Figure PCTCN2022077644-appb-000007
本发明的催化剂材料式(I)简单过滤即可分离，式(I)回收率≥97％。回收的式(I)能循环利用，循环使用10次，催化活性不变。
具体实施方式
实施例1
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乙腈中后加入反应体系。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，CDCl 3)δ：8.49(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2
中间体(V)的制备，进行3个并列的反应，：
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进行并列的缩合反应(每个反应的二胺分别为：a、N-Boc-邻苯二胺；b、N-Boc-1，2-环己二胺；c、N-Boc-1，2-二苯基乙二胺)，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，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 PCTCN2022077644-appb-000008
其收率86％。ESI-MS(m/z):905[M+H] +； 1H NMR(300MHz，CDCl 3)δ： 8.54(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 PCTCN2022077644-appb-000009
收率91％。ESI-MS(m/z):911[M+H] +； 1H NMR(300MHz，CDCl 3)δ：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),7.18-7.07(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)。
中间体Vc
Figure PCTCN2022077644-appb-000010
收率89％。ESI-MS(m/z):1009[M+H] +； 1HNMR(300MHz，CDCl 3)δ：8.54(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),2.76(m,2H),2.57(s,3H),2.03(s,1H),1.41(s,9H)。
实施例3
催化剂(VI)的制备，进行3个并列的反应，：
氮气氛围下，并列将不同的中间体V(实施例2的Va、Vb、Vc)各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，制得各自的催化剂(VI)。用Va制得的催化剂VIa
Figure PCTCN2022077644-appb-000011
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)。
催化剂VIb
Figure PCTCN2022077644-appb-000012
收率为95％， 1H NMRδ：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)。
催化剂VIc
Figure PCTCN2022077644-appb-000013
收率92％； 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4
催化材料式(I)的制备，进行3个并列的反应，：
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，再并列加入实施例3的3个中间体(VI)(2.0mmol)的20mL乙腈溶液，加热回流48h，冷却，过滤，水洗，制得MCM-41负载的催化材料式(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催化剂式(I)负载量为0.90mmol/g。
实施例5
N 2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，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,D 2O):δ3.83(s,1H),1.10(s,9H)。
实施例6
使用不同的α-氨基砜
Figure PCTCN2022077644-appb-000014
参照实施例5合成更多氨基酸，结果如下表1：
编号 催化材料I 氨基砜的R1 产物 收率 ee值
1 Ib 环己基 (R)-环己基甘氨酸盐酸盐 76％ 96％
2 Ic 苯基 (R)-苯基甘氨酸盐酸盐 81％ 99％
3 Ic 3-氯苯基 (R)-3-氯苯基甘氨酸盐酸盐 72％ 96％
实施例7
按实施例5操作，考察催化材料式(I)的循环利用次数。结果如下：
表2式(Ia)的循环利用次数
Figure PCTCN2022077644-appb-000015

Claims (6)

  1. 手性冠醚催化剂，其结构如式(VI)所示：
    Figure PCTCN2022077644-appb-100001
    R2与R3均为苯基，或者R2与R3连接形成A环，A环为苯环或环己烷。
  2. 中间体V，其结构选自下述任一个：
    Figure PCTCN2022077644-appb-100002
  3. 通过MCM-41负载权利要求1所述催化剂的介孔材料，其结构如式(I)所示：
    Figure PCTCN2022077644-appb-100003
  4. 如权利要求3所述的介孔材料在催化合成式VII的(R)-氨基酸中的应用，
    Figure PCTCN2022077644-appb-100004
    R1为苯基、3-氯苯基、叔丁基或环己 基。
  5. 如权利要求4所述的应用，其中，所述式VII氨基酸由α-氨基砜与KCN合成制得。
  6. 权利要求1所述催化剂的制备方法，包括：脱除权利要求2所述中间体V的羟基保护基。
PCT/CN2022/077644 2021-02-24 2022-02-24 催化剂及其应用 WO2022179557A1 (zh)

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