CN109503737B - 一种聚苯乙烯固载的手性二胺类配体及其制备方法和应用 - Google Patents

一种聚苯乙烯固载的手性二胺类配体及其制备方法和应用 Download PDF

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CN109503737B
CN109503737B CN201811376441.6A CN201811376441A CN109503737B CN 109503737 B CN109503737 B CN 109503737B CN 201811376441 A CN201811376441 A CN 201811376441A CN 109503737 B CN109503737 B CN 109503737B
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张宝华
史兰香
刘斯婕
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Shijiazhuang University
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Abstract

本发明公开了一种聚苯乙烯固载的手性二胺类配体及其制备方法和应用。其结构如式（I）所示。式（I）的制备方法包括以下步骤：a.化合物（1）与盐酸氮芥在碱作用下反应制得（2）；b.（2）与聚乙烯苯磺酰氯反应，制得（3）；c.（3）与卤代烃反应得（4），d.（4）脱Boc保护基制得聚苯乙烯固载的手性二胺类配体式（I）。式（I）与钌、铑、铱络合形成催化剂，能在水中高效催化芳香酮、亚胺的不对称转移氢化反应并能循环利用。

Description

一种聚苯乙烯固载的手性二胺类配体及其制备方法和应用
技术领域
本发明涉及催化有机合成领域，具体地说，涉及一种聚苯乙烯固载的手性二胺类配体及其制备方法和应用。
背景技术
手性醇和胺是重要的精细化工中间体，也是重要的手性砌块。对前手性酮或亚胺的不对称催化氢化和不对称催化转移氢化是获得这两类化合物的重要方法。相比于不对称催化氢化，不对称催化转移氢化更安全。不对称催化转移氢化所用的催化剂一般为手性氨基醇或手性二胺与过渡金属钌、铑、铱形成的络合物。最注目的是Noyori开发的钌-手性二胺配合物Ru-TsDPEN催化剂，以2-PrOH/KOH, HCO2H/Et3N为氢源，在温和的条件下，可将前手性酮或亚胺还原成相应的手性醇或胺，收率和对映选择性高。但以水为溶剂的反应更受青睐。随后，科学家对手性1，2-二苯基乙二胺或手性1，2-环己二胺进行修饰，如引入磺酸基、磺酸钠基、磺酸季铵盐基等，使配体与过渡金属钌、铑、铱形成配合物后，能够在水中理想的完成前手性酮或亚胺的不对称催化转移氢化反应。为了更好的实现催化剂的回收利用，Deng将TsDPEN负载在硅胶上，Xiao将TsDPEN负载在PEG上，与过渡金属钌形成配合物，分别在水中完成了前手性酮的不对称催化转移氢化反应（如苯乙酮还原产物收率均>99%, ee值分别为91%, 94%），且催化剂能够循环利用。Itsuno用对位磺化的聚苯乙烯支撑水溶性TsDPEN类配体，再将聚苯乙烯对位的磺酸基团制成钠盐或季铵盐，与钌形成配合物后，以甲酸钠为氢源，在水中可以高对映选择性的将酮还原为醇（如苯乙酮还原产物ee值为90%）。尽管如此，能够在水中温和的实现前手性酮或亚胺高收率、高对映选择性的不对称催化转移氢化反应、且能循环利用的手性配体仍然很少，需要加紧开发。
发明内容
本发明的目的在于提供一种聚苯乙烯固载的手性二胺类配体及其制备方法和应用。
本发明提供的一种聚苯乙烯固载的手性二胺类配体，结构如式(I)所示：
Figure DEST_PATH_IMAGE001
式中，R为H，烃基；X为Cl，Br；
Figure DEST_PATH_IMAGE003
为聚苯乙烯（含2%二乙烯基苯）。
本发明还提供所述聚苯乙烯固载的手性二胺类配体的制备方法，包括以下步骤：
a.（R, R）-N-Boc-N’-（4-氨基苯磺酰）-1，2-环己二胺（1）与盐酸氮芥在碱作用下反应制得中间体（2）；
b.中间体（2）与聚乙烯苯磺酰氯反应，制得中间体（3）；
c.中间体（3）与卤代烃反应制得中间体（4）；
d. 中间体（4）再用HX/THF脱Boc保护基制得聚苯乙烯固载的手性二胺类配体(I)。
其合成路线如下所示：
Figure 739758DEST_PATH_IMAGE004
式中，R为H，烃基；X为Cl，Br；
Figure 656898DEST_PATH_IMAGE003
为聚苯乙烯（含2%二乙烯基苯）。
本发明还提供了所述的聚苯乙烯固载的手性二胺类配体的应用。式(I)分别与[RuCl2(p-cymene)]2,[Cp*RhCl2]2和[(C5Me5)IrCl2]络合生成Ru-(I)，Rh-(I)和Ir-(I)催化剂，这些催化剂在水中能催化芳香酮、亚胺的不对称转移氢化反应，高收率高对映选择性的获得手性醇或手性胺，且催化剂可以回收循环利用。
上述应用步骤为：N2保护下，将式(I)（0.012mmol），[RuCl2(p-cymene)]2或[Cp*RhCl2]2或[(C5Me5)IrCl2]（0.005mmol）加入2mL脱气蒸馏水中溶解，40℃下反应1h，原位生成Ru-(I)或Rh-(I)或Ir-(I)催化剂后，加入氢源（5mmol),搅拌溶解，再加入芳香酮或亚胺（1mmol)反应，TLC监测反应进程，反应完毕，冷至室温，过滤，洗涤，干燥，回收催化剂，循环利用。滤液用正己烷萃取，干燥，过滤，减压浓缩，柱层析纯化，得到相应的手性醇或胺。其反应式如下所示：
Figure DEST_PATH_IMAGE005
式中，R1，R2，R3各自独立为烷基，芳基；亚胺为环状或非环状结构。
在上述步骤中，所述的氢源为HCO2Na，HCO2H/Et3N。
本发明的有益效果主要体现在：所述的聚苯乙烯固载的手性二胺类配体与钌、铑、铱络合形成催化剂，可在水中高收率高对映选择性催化芳酮、亚胺的不对称转移氢化反应，催化剂易与产物分离，并能循环利用，以水为溶剂，绿色环保。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：
实施例1
中间体（2）的制备
将369mg(1mmol)化合物（1），214mg(1.2mmol)盐酸氮芥，190mg(1.8mmol)Na2CO3和10mL氯仿加入反应器中，回流反应8h。向体系中加入10mL水，分层，水相用三氯甲烷萃取，干燥，过滤，浓缩，柱层析纯化，得到中间体（2）337mg，收率77%。[α]D 23 = + 69.9° (c 0.5,C2H5OH)。IR（KBr）v：3477，3380，1689，1156cm-1。
实施例2
中间体（3）的制备
将1.35g(4mmol)中间体（2）加入10mL二氯甲烷中，冷至0℃，加入213mg(1mmol)聚乙烯苯磺酰氯（含2%二乙烯基苯， Cl = 4.70 mmol / g），保温反应2h，升至室温，反应24h。过滤，依次用二氯甲烷、CH3OH-H2O，CH3OH洗涤，50℃真空干燥5h，得固载聚合物中间体（3）0.45g。
实施例3
将0.45g(1mmol)固载聚合物（3）中加入7mL甲醇，冷至0℃，再加入溴甲烷（1mmol）的甲醇溶液4mL，密封，摇匀，冰箱放置48h。过滤，甲醇洗涤，50℃真空干燥5h，得中间体（4a）0.52g(R=CH3,X=Br)。
用溴乙烷代替溴甲烷，其它操作不变，制得中间体（4b）0.52g(R=C2H5,X=Br)。
用氯丙烷代替溴甲烷，其它操作不变，制得中间体（4c）0.5g (R=C3H7,X=Cl)。
实施例4
将0.52g中间体（4a）加入到10mL1mol/L的HBr/THF溶液中，室温搅拌2h，过滤，THF洗涤，50℃真空干燥5h，得配体（Ia）0.46g。负载量为2.31mmol/g(R=CH3,X=Br)。
用中间体（4b）按上述方法操作，得配体（Ib）0.45g。负载量为2.29mmol/g(R=C2H5,X=Br)。
将中间体（4c）0.50g加入到10mL1mol/L的HCl/THF溶液中，室温搅拌5h，过滤，THF洗涤，50℃真空干燥5h，得配体（Ic）0.43g。负载量为2.27mmol/g(R=C3H7,X=Cl)。
将0.45g(1mmol)固载聚合物（3）加入到10mL1mol/L的HCl/THF溶液中，室温搅拌5h，过滤，THF洗涤，50℃真空干燥5h，得配体（Id）0.43g。负载量为2.28mmol/g(R=H,X=Cl)。
实施例5
N2保护下，将5.19mg(0.012mmol)配体(Ia)，3.1mg(0.005mmol)[RuCl2(p-Cymene)]2加入2mL脱气蒸馏水中溶解，40℃下反应1h，原位生成催化剂Ru-(Ia)后，加入520mg(5mmol)HCO2Na,搅拌溶解，再加入120mg(1mmol)苯乙酮，反应4h，TLC监测反应完毕，冷至室温，过滤，洗涤，干燥，回收催化剂Ru-(Ia)，循环利用。滤液用正己烷萃取，干燥，过滤，减压浓缩，柱层析纯化，得到相应的1-苯基乙醇，收率100%，ee值94%。
实施例6
N2保护下，将5.29mg(0.012mmol)配体(Ib)，1.99mg(0.005mmol)[(C5Me5)IrCl2]加入2mL脱气蒸馏水中溶解，40℃下反应1h，原位生成催化剂Ir-(Ib)后，加入230mg(5mmol)HCO2H和505mg(5mmol)Et3N,搅拌，再加入199mg(1mmol)4-溴苯乙酮，反应3.5h，TLC监测反应完毕，冷至室温，过滤，洗涤，干燥，回收催化剂Ir-(Ib)，循环利用。滤液用正己烷萃取，干燥，过滤，减压浓缩，柱层析纯化，得到相应的1-(4-溴苯基)-乙醇，收率100%，ee值96%。
实施例7
N2保护下，将5.24mg(0.012mmol)配体(Ic)，3.09mg(0.005mmol)[Cp*RhCl2]2加入2mL脱气蒸馏水中溶解，40℃下反应1h，原位生成催化剂Rh-(Ic)后，加入230mg(5mmol)HCO2H和505mg(5mmol)Et3N,搅拌，再加入341mg(1mmol)3，4-二氢罂粟碱，反应7h，TLC监测反应完毕，冷至室温，过滤，洗涤，干燥，回收催化剂Rh-(Ic)，循环利用。滤液用甲苯萃取，干燥，过滤，减压浓缩，柱层析纯化，得到1，2，3，4 -四氢罂粟碱，收率99%，ee值96%。
实施例8
催化剂循环利用次数研究
以实施例5，实施例6，实施例7为例，分别考察催化剂Ru-(Ia)，Ir-(Ib)和Rh-(Ic)的循环利用次数（表1）。结果显示，3种催化剂循环利用7次，活性均不减。
Figure DEST_PATH_IMAGE007

Claims (6)

1.一种聚苯乙烯固载的手性二胺类配体，其特征在于，其结构如式(I)所示：
Figure FDA0002806934640000011
式中，R为H，烃基；X为Cl，Br；·为含2％二乙烯基苯的聚苯乙烯。
2.根据权利要求1所述的聚苯乙烯固载的手性二胺类配体的制备方法，其特征在于，包括以下步骤：
a.(R,R)-N-Boc-N’-(4-氨基苯磺酰基)-1，2-环己二胺(1)与盐酸双(2-氯乙基)胺在碱作用下反应制得中间体(2)；
b.中间体(2)与含2％二乙烯基苯的聚苯乙烯磺酰氯反应，制得中间体(3)；
c.中间体(3)与卤代烃反应制得中间体(4)；
d.中间体(4)用HX/THF脱Boc保护基制得聚苯乙烯固载的手性二胺类配体式(I)。
其合成路线如下所示：
Figure FDA0002806934640000021
式中，R为H，烃基；X为Cl，Br；·为含2％二乙烯基苯的聚苯乙烯。
3.根据权利要求2所述的聚苯乙烯固载的手性二胺类配体的制备方法，其特征在于，步骤a所述的碱为Na2CO3,K2CO3,K3PO4。
4.根据权利要求1所述的聚苯乙烯固载的手性二胺类配体的应用，其特征在于，式(I)分别与[RuCl2(p-cymene)]2,[Cp*RhCl2]2和[(C5Me5)IrCl2]络合生成Ru-(I)，Rh-(I)和Ir-(I)催化剂，这些催化剂在水中能催化芳香酮、亚胺的不对称转移氢化反应，高收率高对映选择性的获得手性醇或手性胺，且催化剂可以回收循环利用。
5.根据权利要求4所述的聚苯乙烯固载的手性二胺类配体的应用，其特征在于，芳香酮、亚胺的不对称催化转移氢化反应包括以下步骤：N2保护下，将0.012mmol式(I)，0.005mmol的[RuCl2(p-cymene)]2或[Cp*RhCl2]2或[(C5Me5)IrCl2]加入2mL脱气蒸馏水中溶解，40℃下反应1h，原位生成Ru-(I)或Rh-(I)或Ir-(I)催化剂后，加入5mmol氢源,搅拌溶解，再加入1mmol芳香酮或亚胺反应，TLC监测反应进程，反应完毕，冷至室温，过滤，洗涤，干燥，回收催化剂，循环利用，滤液用正己烷萃取，干燥，过滤，浓缩，柱层析纯化，得到相应的手性醇或胺。其反应式如下所示：
Figure FDA0002806934640000031
式中，R1，R2，R3各自独立为烷基，芳基；亚胺为环状或非环状结构。
6.根据权利要求5所述的聚苯乙烯固载的手性二胺类配体的应用，其特征在于所述的氢源为HCO2Na，HCO2H/Et3N。
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