CN109574946B - 二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途 - Google Patents

二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途 Download PDF

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CN109574946B
CN109574946B CN201811512958.3A CN201811512958A CN109574946B CN 109574946 B CN109574946 B CN 109574946B CN 201811512958 A CN201811512958 A CN 201811512958A CN 109574946 B CN109574946 B CN 109574946B
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diphenylamine
oxazoline
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夏远志
陈建辉
刘红梅
况锦强
陈欣娅
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Abstract

本发明提供的二苯胺‑胺‑噁唑啉配体，为式(1)所述的化合物或者为式(1)所述化合物的对映体或消旋体，其中，R1和R2分别独立为C1～C10的烃基、苄基、苯基或取代的苯基、杂芳基中的一种；R3为H或甲基。本发明同时公开了合成方法及其金属配合物和用途，以提供能够通过简单的合成线路实现高合成产率的催化剂，并确保其对烯烃和酮的不对称氢化和氢转移反应中具有非常高的催化活性。

Description

二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途
技术领域
本发明涉及催化剂技术领域，尤其涉及二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途。
背景技术
过渡金属催化的不对称合成反应是制备手性化合物最为高效的方式之一，也是工业和学术界共同关注的热门领域。自从化学家们发现可以通过手性配体的结合来调节过渡金属在不对称催化反应中的活性和选择性之后，手性配体的设计就成为了过渡金属催化不对称合成领域的核心内容之一。至今已有数以千计的手性配体被发展出来应用于不对称合成反应，其中也涌现了一些具有广泛催化活性的优势手性配体[(a)Q.Zhou,PrivilegedChiralLigandsandCatalysts,Wiley-VCH,Weinheim,2011；b)T.P.Yoon,E.N.Jacobsen,Science2003,299,1691；c)A.faltz,W.J.DruryIII,PNAS2004,101,5723.]。手性噁唑啉可以由自然界常见的氨基酸来制备，是一类常见的手性配体砌块，如优势手性配体PyBox、BOX、PHOX等，可以和很多金属形成络合物催化许多类型的反应[(a)D.Rechavi,M.Lemaire,Chem.Rev.2002,102,346；(b)G.Desimoni,G.Faita,P.Quadrelli,Chem.Rev.2003,103,3119.]。因此，基于噁唑啉砌块构建不同的手性配体骨架引起了化学工作者的广泛兴趣，也由此实现了一些列高效的不对称催化转化，推动了不对称催化领域的发展[(a)S.Zhu,X.Song,Y.Li,Y.Cai,Q.Zhou,J.Am.Chem.Soc.2010,132,16374；(b)Y.Zhang,F.Wang,W.Zhang,J.Org.Chem.2007,72,9208；(c)B.Cheng,W.Liu,Z.Lu,J.Am.Chem.Soc.2018,140,501；(d)J.Guo,B.Cheng,X.Shen,Z.Lu,J.Am.Chem.Soc.2017,139,15316.]。
烯烃、酮等不饱和有机化合物的不对称氢化和氢转移等还原反应是高效的合成光学活性分子的手段，具有原子经济性高、操作简单、清洁绿色等优点，在化工工业大生产中有着重要的应用。现有的催化体系主要是基于铑、钌、铱、钯等铂族贵金属和手性膦配体的组合。铂族金属在地壳中储量较少(总计可开采储量为仅7.1万吨)，属于战略性资源；同时手性膦配体的合成效率是一个难题。
因此，开发一种新的二苯胺-胺-噁唑啉配体，实现铁和钴等地球丰产过渡金属在不对称催化领域的广发应用，并进一步研究其高效合成的线路，不但具有迫切的研究价值，也具有良好的经济效益和工业应用潜力，这正是本发明得以完成的动力所在和基础。
发明内容
为了克服上述所指出的现有技术的缺陷，本发明人对此进行了深入研究，在付出了大量创造性劳动后，从而完成了本发明。
具体而言，本发明所要解决的技术问题是：提供二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途，以提供能够通过简单的合成线路实现高合成产率的催化剂，并确保其对烯烃和酮的不对称氢化和氢转移反应中具有非常高的催化活性。
为解决上述技术问题，本发明的技术方案是：
第一方面，本发明提供了二苯胺-胺-噁唑啉配体，其为式(1)所述的化合物
Figure GDA0003785642980000021
或者为式(1)所述化合物的对映体或消旋体，其中，
R1和R2分别独立为C1～C10的烃基、苄基、苯基或取代的苯基、杂芳基；R3为H或甲基。
其中，所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基。
本发明中，作为一种优选的技术方案，R1优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
本发明中，作为一种优选的技术方案，R2优选为取代的苯基和环己基。其中，取代的苯基中取代基为C1～C6的烃基、烃氧基以及卤素，取代基数量为1-5。
第二方面，本发明提供了上述二苯胺-胺-噁唑啉配体的合成方法，包括如下步骤：
第一步：溶剂中，邻溴苯甲醛和胺在对甲苯磺酸(p-TsOH)的催化下缩合得到相应的亚胺，随后经氢化铝锂(LiAlH4)还原得到中间体—N-取代的邻溴苄胺(A)；
第二步：溶剂中，邻氨基苯腈和手性胺基醇在Zn(OTf)2的催化下缩合得到中间体—邻位噁唑啉取代的苯胺(B)；
第三步：惰性气氛下，二氧六环溶剂中，邻溴苄胺(A)和苯胺(B)在醋酸钯的催化下偶联得到产物二苯胺-胺-噁唑啉配体(1)。
本发明中，作为作为一种优选的技术方案，第一步和第二步中的溶剂为甲苯溶剂。
本发明中，作为作为一种优选的技术方案，第三步中的溶剂为二氧六环溶剂。
其合成路线如下：
Figure GDA0003785642980000041
第三方面，本发明提供了二苯胺-胺-噁唑啉金属配合物，该配合物是由化合物1与元素周期表的过渡族的过渡金属形成，且具有如式(2)所述的通式
Figure GDA0003785642980000042
其中，M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir中的一种；
X选自卤化物(F、Cl、Br、I)、拟卤化物(氰化物、氰酸、盐、异氰酸盐)、羧酸、磺酸、膦酸的阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根)中的任意一种；
E为H或甲基；
n1为X的个数，为0、1、2、3；
n2为E的个数，为0或1。
R1和R2分别独立为C1～C10的烃基、苄基、苯基或取代的苯基、杂芳基；R3为H或甲基。
其中，所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基。
本发明中，作为一种优选的技术方案，R1优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
本发明中，作为一种优选的技术方案，R2优选为取代的苯基和环己基。其中，取代的苯基中取代基为C1～C6的烃基、烃氧基以及卤素，取代基数量为1-5。
第四方面，本发明提供了二苯胺-胺-噁唑啉配体以及二苯胺-胺-噁唑啉金属配合物的用途，是指利用催化量的至少一种二苯胺-胺-噁唑啉配体或二苯胺-胺-噁唑啉金属配合物作为催化剂通过催化反应制备光学选择性有机化合物。例如可以以二苯胺-胺-噁唑啉金属配合物催化三取代烯烃的不对称氢化反应及酮的不对称氢转移反应。
采用了上述技术方案后，本发明的有益效果是：
本发明提供了一种新型二苯胺-胺-噁唑啉配体，二苯胺-胺-噁唑啉配体可以独立用于制备手性或非手性有机化合物，也可以与过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir形成稳定的金属配合物，该金属配合物能够应用于不对称催化反应，特别是对烯烃和酮的不对称氢化和氢转移反应中具有非常高的催化活性。本发明还提供了高效的合成路线，两步总产率均在80％以上。
本发明还提供了化合物1应用于金属催化不对称反应的用途，通过与金属预配位形成的金属催化剂或与金属盐现场生成金属催化剂，化合物1可以用于制备手性或非手性有机化合物。可根据本发明制备的手性或非手性有机化合物是活性物质或用于制备该物质的中间物，特别是在香料和增香剂、药物制剂、农用化学品的生产方面。
具体实施方式
下面结合具体的实施例对本发明进一步说明。但这些例举性实施方式的用途和目的仅用来例举本发明，并非对本发明的实际保护范围构成任何形式的任何限定，更非将本发明的保护范围局限于此。
二苯胺-胺-噁唑啉配体，其为式(1)所述的化合物
Figure GDA0003785642980000061
或者为式(1)所述化合物的对映体或消旋体，其中，R1和R2分别独立为C1～C10的烃基、苄基、苯基或取代的苯基、杂芳基；R3为H或甲基。
上述二苯胺-胺-噁唑啉配体的合成方法，包括如下步骤：
第一步：室温，反应瓶内依次加入邻溴苯甲醛(20mmol)、甲苯(30mL)、胺(22mmol)和甲苯磺酸一水合物(1mmol)，升温至回流反应12小时；随后冷却至室温，硅藻土抽滤，滤液减压旋转蒸发除去溶剂得到相应的亚胺(黄色胶状物)。
另取一三口反应瓶，依次加入氢化铝锂(22mmol)、四氢呋喃(20mL)，0℃、氮气氛下滴加亚胺/四氢呋喃(20mL)溶液，滴加结束后升温至回流反应12小时；
随后冷却至室温，缓慢滴加饱和氯化铵溶液猝灭反应，加入乙酸乙酯(20mL)和饱和食盐水(10mL)，分液，水相再用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥后减压旋转蒸发除去溶剂得到中间体A，反应方程式如下：
Figure GDA0003785642980000062
中间体A的检测结果如下：
Figure GDA0003785642980000063
无色油状液体，产率为92％。1H NMR:(500.1MHz,CDCl3)δ7.57(d,J＝8.0Hz,1H),7.36(d,J＝7.6Hz,1H),7.28-7.22(m,1H),7.17-7.10(m,1H),6.99(d,J＝7.6Hz,1H),6.88-6.81(m,2H),4.20(s,2H),2.26(s,6H).
Figure GDA0003785642980000071
1H NMR:(500.1MHz,CDCl3)δ7.58(d,J＝8.0Hz,1H),7.42(d,J＝7.6Hz,1H),7.32-7.25(m,1H),7.19-7.04(m,4H),4.12(s,2H),3.43(br,1H),3.35-3.23(m,2H),1.21(d,J＝7.0Hz,12H)；
第二步：室温，反应瓶内依次加入邻氨基苯腈(10mmol)、甲苯(10mL)、手性胺基醇(11mmol)和Zn(OTf)2(1mmol)，升温至回流反应24小时，冷却至室温，减压浓缩后柱层析分离得到中间体B，反应方程式为：
Figure GDA0003785642980000072
第三步：室温，惰性气氛下，反应瓶内依次加入中间体A(11mmol)、二氧六环(20mL)、中间体B(10mmol)、醋酸钯(0.5mmol)、双(2-二苯基磷苯基)醚(0.6mmol)和叔丁醇钠(15mmol)，升温至回流反应24小时，冷却至室温，硅胶短柱抽滤，滤液减压浓缩后经柱层析分离得到产物二苯胺-胺-噁唑啉配体(1)。
Figure GDA0003785642980000073
采用如上的制备方法，根据原料的不同，选择R1、R2的种类，分别可以得到如下的二苯胺-胺-噁唑啉配体(1)：
实施例1
采用如上的制备方法，选择R1、R2的种类，得到如下的二苯胺-胺-噁唑啉配体(1a)，为白色固体，产率为88％。
检测结果如下：
Figure GDA0003785642980000081
1H NMR:(500.1MHz,CDCl3)δ10.39(br,1H),7.77(dd,J＝8.0,1.6Hz,1H),7.47-7.38(m,2H),7.32-7.25(m,1H),7.24-7.07(m,7H),7.02(d,J＝8.4Hz,1H),6.93(d,J＝7.6Hz,2H),6.81-6.75(m,1H),6.75-6.69(m,1H),4.59-4.49(m,1H),4.28(dd,J＝9.0,8.6Hz,1H),4.12-3.99(m,3H),3.01(dd,J＝13.7,5.8Hz,1H),2.70(dd,J＝13.7,8.2Hz,1H),2.18(s,6H)；HRMSCalcdfor[C31H31N3O+H]+:462.2540；found:462.2544.
实施例2
采用如上的制备方法，选择R1、R2的种类，得到如下的二苯胺-胺-噁唑啉配体(1b)，为白色固体，产率为87％。
检测结果如下：
Figure GDA0003785642980000082
1H NMR:(399.9MHz,CDCl3)δ10.43(br,1H),7.78(dd,J＝8.0,1.6Hz,1H),7.47(d,J＝7.6Hz,1H),7.44(d,J＝8.0Hz,1H),7.31-7.25(m,1H),7.24-7.17(m,1H),7.16-7.09(m,1H),7.01(d,J＝8.4Hz,1H),6.94(d,J＝7.6Hz,2H),6.83-6.75(m,1H),6.75-6.69(),4.38-4.28(m,1H),4.15(1,J＝13.6Hz,2H),4.10-3.97(m,2H),3.35(br,1H),2.18(s,6H),1.78-1.65(m,1H),0.92(d,J＝6.8Hz,3H),0.85(d,J＝6.8Hz,3H)；13CNMR:(125.8MHz,CDCl3)δ13CNMR:(125.8MHz,CDCl3)delta163.7,146.8,146.0,139.6,134.9,131.9,130.0,129.9,129.8,128.6,128.0,124.3,124.2,122.0,116.6,113.0,110.2,72.9,68.8,49.0,33.0,18.9,18.5,18.3.HRMS Calcdfor[C27H31N3O+H]+:414.2545；found:414.2550.
实施例3
采用如上的制备方法，选择R1、R2的种类，得到如下的二苯胺-胺-噁唑啉配体(1c)，为白色固体，产率为88％。
检测结果如下：
Figure GDA0003785642980000091
1H NMR:(399.9MHz,CDCl3)δ10.41(s,1H),7.79(dd,J＝7.8,1.6Hz,1H),7.57(dd,J＝7.8,1.2Hz,1H),7.41(d,J＝7.8Hz,1H),7.36-7.27(m,1H),7.24-7.16(m,2H),7.08-6.99(m,3H),6.94(d,J＝8.4Hz,1H),6.75-6.68(m,1H),4.26(dd,J＝9.6,8.4Hz,1H),4.13(dd,J＝8.4,8.0Hz,1H),4.10-4.00(m,3H),3.31(br,1H),3.26-3.13(m,2H),1.11(d,J＝7.0Hz,6H),1.07(d,J＝7.0Hz,6H),0.85(s,9H)；13CNMR:(125.8MHz,CDCl3)δ163.7,147.2,143.1,142.8,139.4,135.7,132.0,129.9,129.8,128.1,125.3,125.0,123.8,123.4,116.5,112.7,109.9,76.3,67.0,52.3,33.8,27.6,25.9,24.2,24.1；HRMSCalcdfor[C32H41N3O+H]+:484.3328；found:484.3329.
实施例4
采用如上的制备方法，选择R1、R2的种类，得到如下的二苯胺-胺-噁唑啉配体(1d)，为白色固体，产率为89％。
检测结果如下：
Figure GDA0003785642980000101
1H NMR:(399.9MHz,CDCl3)δ10.45(br,1H),7.78(dd,J＝8.0,1.6Hz,1H),7.46(d,J＝8.0Hz,1H),7.39(dd,J＝7.6,1.2Hz,1H),7.32-7.25(m,1H),7.25-7.18(m,1H),7.12-7.06(m,1H),7.04(d,J＝8.4Hz,1H),6.94(d,J＝7.6Hz,2H),6.82-6.76(m,1H),6.76-6.69(m,1H),4.14(s,2H),4.00(s,2H),3.40(br,1H),2.20(s,6H),1.27(s,6H).HRMSCalcdfor[C26H29N3O+H]+:400.2383；found:400.2388。
实施例5
二苯胺-胺-噁唑啉-铁配合物的合成
Figure GDA0003785642980000102
室温，氮气氛下，反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol)，干燥四氢呋喃(THF)(5mL)和氯化亚铁(FeCl2)(0.95mmol)，反应液逐渐变棕绿色悬浊液，搅拌反应5小时后抽滤，滤饼用乙醚洗涤三次(每次5mL)，收集滤饼，油泵抽干得到棕绿色粉末状固体(2a)，产率为88％。
检测结果如下：
Figure GDA0003785642980000103
Anal.CalcdforC31H31Cl2FeN3O:C,63.29；H,5.31；N,7.14；FoundC,63.00；H,5.36；N,6.99.
实施例6
二苯胺-胺-噁唑啉-钴配合物的合成
Figure GDA0003785642980000111
室温，氮气氛下，反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol)，干燥四氢呋喃(THF)(5mL)和氯化钴(CoCl2)(0.95mmol)，反应液逐渐变绿色悬浊液，搅拌反应5小时后抽滤，滤饼用乙醚洗涤三次(每次5mL)，收集滤饼，油泵抽干得到绿色粉末状固体(2b)，产率为96％。
检测结果如下：
Figure GDA0003785642980000112
Anal.CalcdforC31H31Cl2CoN3O:C,62.95；H,5.28；N,7.10；FoundC,62.88；H,5.11；N,6.92.
实施例7
二苯胺-胺-噁唑啉-锰配合物的合成
Figure GDA0003785642980000113
室温，氮气氛下，反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol)，干燥四氢呋喃(THF)(5mL)和氯化锰(MnCl2)(0.95mmol)，反应液逐渐变浅黄色悬浊液，搅拌反应5小时后抽滤，滤饼用乙醚洗涤三次(每次5mL)，收集滤饼，油泵抽干得到黄白色粉末状固体(2c)，产率为94％。
检测结果如下：
Figure GDA0003785642980000121
Anal.CalcdforC31H31Cl2MnN3O:C,63.38；H,5.32；N,7.15；FoundC,62.99；H,5.01；N,6.96.
实施例8
二苯胺-胺-噁唑啉-锌配合物的合成
Figure GDA0003785642980000122
室温，氮气氛下，反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol)，干燥四氢呋喃(THF)(5mL)和氯化锌(ZnCl2)(0.95mmol)，反应液逐渐变白色悬浊液，搅拌反应5小时后抽滤，滤饼用乙醚洗涤三次(每次5mL)，收集滤饼，油泵抽干得到白色粉末状固体(2d)，产率为85％。
检测结果如下：
Figure GDA0003785642980000131
Anal.CalcdforC31H31Cl2ZnN3O:C,62.28；H,5.23；N,7.03；FoundC,62.13；H,5.20；N,6.99.
实施例9
催化三取代烯烃的不对称氢化反应
Figure GDA0003785642980000132
室温，氮气氛下，在一干燥的反应试管中加入(手性)二苯胺-胺-噁唑啉-CoCl2配合物(2b)(0.005mmol)，烯烃(0.5mmol)，抽真空后反应管连接一个氢气球，随后注射加入干燥的甲苯(1mL)和三乙基硼氢化钠溶液(0.010mmol)，室温下搅拌1小时后柱层析分离得到氢化产物。
检测结果如下：
Figure GDA0003785642980000133
无色油状液体，>99％产率，[α]20 D＝25.8(c0.86,CHCl3)，95.2％ee；1H NMR:(400.1MHz,CDCl3)δ7.09(d,J＝8.4Hz,2H),6.83(d,J＝8.4Hz,2H),3.78(s,3H),2.60-2.48(m,1H),1.61-1.49(m,2H),1.21(d,J＝7.0Hz,3H),0.81(t,J＝7.4Hz,3H).
Figure GDA0003785642980000134
无色油状液体，>99％产率，[α]20 D＝22.2(c0.89,CHCl3)，94.6％ee；1H NMR:(400.1MHz,CDCl3)δ7.14-7.03(m,4H),2.65-2.49(m,1H),2.31(s,3H),1.64-1.52(m,2H),1.22(d,J＝6.8Hz,3H),0.82(t,J＝7.2Hz,3H).
Figure GDA0003785642980000141
无色油状液体，>99％产率，[α]20 D＝23.2(c0.96,CHCl3)，93.2％ee；1H NMR:(400.1MHz,CDCl3)δ7.32-7.23(m,2H),7.22-7.13(m,3H),2.72-2.59(m,1H),1.62-1.48(m,2H),1.34-1.08(m,7H),0.85(t,J＝6.8Hz,3H).
Figure GDA0003785642980000142
无色油状液体，>99％产率，[α]20 D＝19.4(c1.01,CHCl3)；95.0％ee；1H NMR:(400.1MHz,CDCl3)δ7.32-7.22(m,2H),7.22-7.11(m,3H),2.84-2.70(m,1H),1.58-1.31(m,3H),1.20(d,J＝7.0Hz,3H),0.87(d,J＝6.0Hz,3H),0.84(d,J＝6.0Hz,3H).
实施例10
氯化钴催化三取代烯烃的氢化反应(对比实施例)
Figure GDA0003785642980000143
室温，氮气氛下，在一干燥的反应试管中加入CoCl(0.005mmol)，烯烃(0.5mmol)，抽真空后反应管连接一个氢气球，随后注射加入干燥的甲苯(1mL)和三乙基硼氢化钠溶液(0.010mmol)，室温下搅拌1小时后气质联用检测未发现氢化产物。
实施例11
催化酮的不对称氢转移反应
Figure GDA0003785642980000151
室温，氮气氛下，在一干燥的反应试管中加入(手性)二苯胺-胺-噁唑啉-CoCl2配合物(2b)(0.005mmol)，酮(0.5mmol)，异丙醇(1mL)和叔丁醇钠(0.025mmol)，然后在40℃下反应12小时后柱层析分离得到氢转移产物。
检测结果如下：
Figure GDA0003785642980000152
油状液体，98％产率，[α]20 D＝+58.5(c0.99,CHCl3)；97.1％ee；1H NMR(CDCl3,400MHz):δ7.27-7.40(m,4H),7.24-7.30(m,1H),4.84-4.93(m,1H),1.93(br,1H),1.49(d,J＝6.2Hz,3H).
Figure GDA0003785642980000153
油状液体，92％产率，[α]20 D＝+55.4(c1.01,CHCl3)；97.7％ee；1H NMR(CDCl3,400MHz):δ7.27(d,J＝7.8Hz,2H),7.16(d,J＝7.8Hz,2H),4.82-4.92(m,1H),2.34(s,3H),1.79(br,1H),1.48(d,J＝6.4Hz,3H).
Figure GDA0003785642980000154
油状液体，94％产率，[α]20 D＝+17.5(c1.1,CHCl3)；97.5％ee；1H NMR(CDCl3,400MHz):δ7.30(d,J＝7.8Hz,2H),6.88(d,J＝7.8Hz,2H),4.82-4.91(m,1H),3.81(s,3H),1.73(br,1H),1.48(d,J＝6.2Hz,3H).
Figure GDA0003785642980000155
油状液体，95％产率，[α]20 D＝+35.5(c1.01,CHCl3)；96.6％ee；1H NMR(CDCl3,400MHz):δ7.27(d,J＝7.6Hz,2H),7.12(d,J＝7.0Hz,2H),4.80-4.90(m,1H),2.46(d,J＝6.8Hz,2H),1.78-1.97(m,2H),1.44-1.53(m,3H),0.85-0.96(m,6H).
Figure GDA0003785642980000161
油状液体，89％产率，[α]20 D＝+44.8(c0.88,CHCl3)；96.0％ee；1H NMR(CDCl3,400MHz):δ7.30-7.41(m,2H),7.03(t,J＝8.6Hz,2H),4.81-4.92(m,1H),1.95(br,1H),1.47(d,J＝6.4Hz,3H).
Figure GDA0003785642980000162
油状液体，97％产率，[α]20 D＝+44.2(c0.93,CHCl3)；96.1％ee；1H NMR(CDCl3,400MHz):δ7.23-7.34(m,4H),4.79-4.87(m,1H),2.30(br,1H),1.44(d,J＝6.4Hz,3H).
Figure GDA0003785642980000163
油状液体，97％产率，[α]20 D＝+35.7(c0.98,CHCl3)；96.0％ee；1H NMR(CDCl3,400MHz):δ7.47(d,J＝8.0Hz,2H),7.25(d,J＝8.0Hz,2H),4.82-4.92(m,1H),1.84(br,1H),1.47(d,J＝6.4Hz,3H).
实施例12
氯化钴催化酮的氢转移反应(对比实施例)
Figure GDA0003785642980000164
室温，氮气氛下，在一干燥的反应试管中加入CoCl2(0.005mmol)，酮(0.5mmol)，异丙醇(1mL)和叔丁醇钠(0.025mmol)，然后在40℃下反应12小时气质联用检测未发现产物。
由以上实施例可知，采用本发明制备得到的二苯胺-胺-噁唑啉-CoCl2配合物能够有效催化烯烃或酮的不对称氢化和氢转移反应。
当理解，这些实施例的用途仅用于说明本发明而非意欲限制本发明的保护范围。此外，也应理解，在阅读了本发明的技术内容之后，本领域技术人员可以对本发明作各种改动、修改和/或变型，所有的这些等价形式同样落于本申请所附权利要求书所限定的保护范围之内。

Claims (6)

1.二苯胺-胺-噁唑啉配体，其特征在于：为式(1)所述的化合物
Figure FDA0003822719440000011
其中，
R1为苄基；R2为2，6-二甲基苯基；R3为H。
2.合成如权利要求1所述二苯胺-胺-噁唑啉配体的方法，其特征在于：包括如下步骤：
第一步：溶剂中，邻溴苯甲醛和胺在对甲苯磺酸的催化下缩合得到相应的亚胺，随后经氢化铝锂还原得到中间体N-取代的邻溴苄胺(A)
Figure FDA0003822719440000012
第二步：溶剂中，邻氨基苯腈和手性胺基醇在Zn(OTf)2的催化下缩合得到中间体邻位噁唑啉取代的苯胺(B)
Figure FDA0003822719440000013
第三步：惰性气氛下，溶剂中，中间体—N-取代的邻溴苄胺(A)和邻位噁唑啉取代的苯胺(B)在醋酸钯的催化下偶联得到产物二苯胺-胺-噁唑啉配体(1)；
其中，
R1为苄基；R2为2，6-二甲基苯基；R3为H。
3.如权利要求2所述的合成方法，其特征在于：第一步和第二步中的溶剂为甲苯溶剂。
4.如权利要求2所述的合成方法，其特征在于：第三步中的溶剂为二氧六环溶剂。
5.二苯胺-胺-噁唑啉金属配合物，其特征在于：该配合物是权利要求1所述的化合物与元素周期表的过渡族的过渡金属形成，且具有如式(2)所述的通式
Figure FDA0003822719440000021
其中，M为过渡金属Co；
X为Cl；
E为H；
n1为2；
n2为1；
R1为苄基；R2为2，6-二甲基苯基；R3为H。
6.如权利要求5所述二苯胺-胺-噁唑啉金属配合物的用途，其特征在于：以所述二苯胺-胺-噁唑啉金属配合物催化三取代烯烃的不对称氢化反应及酮的不对称氢转移反应。
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