CN104327104A - 一种同质异晶手性锌配合物 - Google Patents

一种同质异晶手性锌配合物 Download PDF

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CN104327104A
CN104327104A CN201410533770.2A CN201410533770A CN104327104A CN 104327104 A CN104327104 A CN 104327104A CN 201410533770 A CN201410533770 A CN 201410533770A CN 104327104 A CN104327104 A CN 104327104A
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Abstract

一种手性锌氮配合物，其化学式如下：该配合物的合成方法由四腈乙烯和D-缬氨醇在无水无氧条件下和催化剂无水ZnCl2(42%)时于氯苯溶剂中回流反应36小时分离、纯化，即反应结束后脱去氯苯，加水溶解后用氯仿萃取，萃取相脱溶后用柱层析纯化；将配合物（I）用石油醚及二氯甲烷淋洗，柱层析分离，自然挥发得配合物单晶。该配合物在苯甲醛的烯丙基烷基化反应、Baylis-Hillman反应、亨利反应及硅腈化反应中显示一定的催化性能，其转化率分别达51%，45%，68%及83%。

Description

一种同质异晶手性锌配合物
一、技术领域
本发明涉及一种金属有机配位化合物（配合物）及其制备方法，特别涉及含氮的手性金属有机配合物及其制备方法，确切地说是一种手性锌氮配合物及其合成方法。
二、背景技术
   随着有机化学的发展,金属有机化合物在有机合成中的应用愈来愈广,是现在有机化学中极为活跃的领域之一,已经广泛应用于有机合成反应中。20世纪60年代后期出现的使用手性配体与过渡金属络合物催化的不对称合成反应大大加速了手性药物的研究。化学催化不对称合成法的重要内容便是手性配体及含金属催化剂的设计,从而使反应具有高效和高对映选择性。通常不对称催化剂所用的配体是噁唑啉，近年来噁唑啉锌配合物被广泛合成并取得较好的催化效果。
 
参考文献：
1. Synthesis of highly modular bis(oxazoline) ligands by Suzuki cross-coupling and evaluation as catalytic ligands，Cattoen, Xavier; Pericas, Miquel A. Tetrahedron，65（39），8199-8205；
2.The synthesis of new oxazoline-containing bifunctional catalysts and their application in the addition of  diethylzinc to aldehydes, Coeffard, Vincent; Mueller-Bunz, Helge; Guiry, Patrick J, Organic &  Biomolecular Chemistry, 7(8), 1723-1734；
3. New Bis(oxazolinyl)phenyl-Ruthenium(II) Complexes and Their Catalytic Activity for Enantioselective Hydrogenation and Transfer Hydrogenation of Ketones, Ito, Jun-ichi; Ujiie, Satoshi; Nishiyama, Hisao, Organometallics, 28(2),630-638；
4.Lewis Acid-Catalyzed Enantioselective Hydroxylation Reactions of Oxindoles and β-Keto Esters  Using DBFOX Ligand，Ishimaru, Takehisa; Shibata, Norio; Nagai, Jun; Nakamura, Shuichi; Toru, Takeshi; Kanemasa, Shuji, Journal of the American Chemical Society，128（51）,6488-16489。
 
三、发明内容
本发明旨在提供一种Zn-N金属有机配合物以应用于催化领域，所要解决的技术问题遴选噁唑啉作为配体并合成手性锌氮配合物。
    本发明所称的手性锌配合物是双-（4-异丙基-4,5-二氢化-2-噁唑啉基）-乙腈锌配合物由四腈乙烯制备的由以下化学式所示的配合物：
化学名称：双-（4-异丙基-4,5-二氢化-2-噁唑啉基）-乙腈锌配合物，简称配合物(I)。
 
本手性化合物的合成方法包括反应、分离和纯化，其特征是制备中间体的反应由四腈乙烯和D-缬氨醇在无水无氧条件下和催化剂无水ZnCl2 (51%)时于氯苯溶剂中回流反应72小时分离、纯化，即反应结束后脱去氯苯，加水溶解后用氯仿萃取，萃取相脱溶后用柱层析纯化；
    本配合物（I）的合成方法是四腈乙烯与D-缬氨醇在氯苯溶剂中回流反应72小时；
配合物（I）用二氯甲烷及甲醇（2:1）淋洗，柱层析分离，然后又加入正己烷、三氯甲烷、乙醇及四氢呋喃配置成饱和溶液，自然挥发后得配合物单晶。
   该配合物（I）与申请人在2012年报道的手性配合物是同质异晶配合物，其晶体的晶胞参数不同；本申请化合物的晶胞参数：三斜晶系，a = 12.1660(10) ?，α= 90°；b = 12.1660(10) ?，β= 90°；c = 18.0515(19) ?，γ= 120°；而已报道的化合物晶胞参数如下：单斜晶系，a = 14.90430(10) ? ， a= 90°；b = 15.22040(10) ?，β= 90°；c = 27.3737(2) ?，γ= 90°，而且该配合物比申请人在2012年报道的同质异晶在苯甲醛的烯丙基烷基化反应、Baylis-Hillman反应、亨利反应及硅腈化反应中显示了较好的催化性能，其转化率分别达51%,45%,68%及83%。
  该配合物（I）的反应机理可推测为四腈乙烯在空气中及氯化锌作用下，不稳定，分解成三腈基甲烷，与2分子的D-缬氨醇作用形成双噁唑啉再与氯化锌按照2:1配位，并脱去两分子盐酸。 
 
四、附图说明
图1是配合物 (I) 的单晶衍射图。
五、具体实施方式
（一）手性配合物的制备
1、双-（4-异丙基-4,5-二氢化-2-噁唑啉基）-乙腈锌配合物的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl2 0.54g (3.97mmol), 40mL氯苯, 四腈乙烯1.0g(7.81mmol), D-缬氨醇 10.0g, 将混合物在高温下回流72 h,停止反应,减压以除去溶剂, ,将剩余物用水溶解,并用CHCl3(20mLx2)萃取,有机相用无水硫酸钠干燥,旋转除去溶剂, 将配合物（I）用二氯甲烷及甲醇（2:1）淋洗，柱层析分离，然后又加入正己烷、三氯甲烷、乙醇及四氢呋喃配置成饱和溶液，自然挥发后得配合物单晶；产率72 %；[a]5 D=+305.9o (c=0.20, CH2Cl2)：1HNMR (500MHz, CDCl3, 27℃), δ (ppm) = 4.35(t, 4H), 4.16 (t, J=1Hz, 4H), 3.81～3.83(m, 4H), 1.62～1.66(m, 4H)，0.74～0.87(dd, J=7Hz, 6.5Hz, 24 H); 13C NMR (75 MHz, CDCl3) 170.6(x2), 118.6(x2), 73.0(x4), 68.9(x4), 68.5(x4), 31.8(x4), 19.2(x4), 15.7(x4)。IR :3443(s), 2963(s), 2200(s), 1609(s), 1533(s), 1484(s), 1432(s), 1391(m), 1371(w), 1341(w), 1312(w), 1251(m), 1222(m), 1117(m), 1075(s), 953(m), 744(m), 566(w), 528(w), 457(w); 元素分析：C:56.78%, H, 6.76%, N, 14.30%；
化合物的晶体结构测定：
   在显微镜下选取合适大小的单晶在室温下进行X-射线单晶衍射实验，在293k温度下，在牛津 X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线（λ=0.71073 ?）以ω-θ 扫描方式收集衍射数据。对所得数据进行Lp因子及经验吸收校正，晶体结构由直接法解出，衍射数据还原和结构解析工作分别使用SAINT-5.0和SHELXS-97程序完成。晶体数据如下：
    经验式               C28H40N6ZnO4
      分子量             590.03     
      温度                  293(2) K 
      波长                  0.71073 ? 
      晶系， 空间群         斜方晶形，P3(1)2(1)
      晶胞参数              a = 12.1660(3) ?  alpha = 90 deg. 
                            b = 12.1660?  beta = 90 deg. 
                            c = 18.0515(17) ?   gamma = 90 deg. 
      体积                 2313.9（5）A^3 
      电荷密度              3，  1.270 Mg/m^3 
      吸收 校正参数         0.870 mm^-1 
      单胞内的电子数目      936
      晶体大小               0.155 x 0.101x 0.054 mm 
      Theta 角的范围         1.933 to 25.997 
      HKL的指标收集范围                 -14<=h<=14, -13<=k<14, -12<=22
      收集/独立衍射数据                 30315 [R(int) = 0.0598
      theta = 30.5的数据完整度          100.0%
      吸收校正的方法                    多层扫描
      最大最小的透过率                  0.7457，0.6379
      精修使用的方法                    F^2 的矩阵最小二乘法
      数据数目/使用限制的数目/参数数目  3031/34/201
      精修使用的方法                     1.115
      衍射点的一致性因子                 R1 = 0.0725，ωR2= 0.1338
      可观察衍射的吻合因子               R1 = 0.1582, ωR2 = 0.1416
       绝对构型参数                      -0.001(11)
       差值傅里叶图上的最大峰顶和峰谷    0.478 and -0.415 e.? ^-3
;
 晶体的键长数据：
Zn(1)-N(1)                            1.995(5)
Zn(1)-N(1)#1                        1.995(5)
Zn(1)-N(2)#1                        1.998(5)
Zn(1)-N(2)                            1.998(5)
N(1)-C(1)                             1.282(8)
N(1)-C(3)                             1.475(9)
N(2)-C(9)                             1.292(8)
N(2)-C(11)                           1.470(9)
N(3)-C(8)                             1.165(8)
O(1)-C(1)                             1.356(7)
O(1)-C(2)                             1.432(9)
O(2)-C(9)                             1.343(7)
O(2)-C(10)                           1.447(9)
C(1)-C(7)                             1.410(9)
C(2)-C(3)                             1.516(11)
 ；
 晶体的键角数据：
N(1)-Zn(1)-N(1)#1            129.4(3)
N(1)-Zn(1)-N(2)#1            105.5(2)
N(1)#1-Zn(1)-N(2)#1          95.4(2)
N(1)-Zn(1)-N(2)                  95.4(2)
N(1)#1-Zn(1)-N(2)            105.5(2)
N(2)#1-Zn(1)-N(2)            130.0(3)
C(1)-N(1)-C(3)                 108.7(5)
C(1)-N(1)-Zn(1)                121.3(4)
C(3)-N(1)-Zn(1)                129.3(4)
C(9)-N(2)-C(11)               108.5(5)
C(9)-N(2)-Zn(1)                121.3(4)
C(11)-N(2)-Zn(1)              129.6(4)
C(1)-O(1)-C(2)                 106.9(5)
C(9)-O(2)-C(10)               106.9(6)
N(1)-C(1)-O(1)                 115.4(6)
N(1)-C(1)-C(7)                 129.6(6)
O(1)-C(1)-C(7)                 115.0(6)
O(1)-C(2)-C(3)                 105.2(5)
（三）、烯丙基烷基化反应应用
           
取0.20mmol的配合物I（催化用量为20％）于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.3mL的烯丙基三甲基硅烷，常温搅拌，反应72小时后，进行核磁分析，转化率：51%；1H NMR (300MHz, CDCl3) 7.27～7.33(m, 5H, Ar-H), 5.79～5.80(m, 1H), 5.12～5.17 (m, 2H, -CH2), 4.71（d，J=5Hz，1H）,2.49～2.50(m, 2H)，2.28（s, 1H）。
（四）Baylis-Hillman反应应用
          
取0.20mmol的配合物I（催化用量为20％）于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL丙烯酸甲酯，常温搅拌，反应小72小时后，进行核磁分析，转化率：45%; 1HNMR (300MHz, CDCl3) 7.20～7.41 (m, 5H, Ar-H), 6.30(s, 1H), 5.45 (s, 1H), 3.70(s, 3H), 3.15(s, 1H)。
（五）亨利反应应用
2-硝基-1苯基乙醇的制备
           
取0.20mmol的配合物I（催化用量为20％）于25mL的小烧瓶中，加入2毫升的无水甲醇溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL的硝基甲烷，常温搅拌，反应小72小时后，进行核磁分析，转化率：68 %；1H NMR (300MHz, CDCl3) 7.28～7.32 (m, 5H, Ar-H), 5.32～5.35(d, J=9.18Hz, 1H, -CH), 4.38～4.56 (m, 2H, -CH2), 3.89(br, 1H, -OH)。
（六）、腈硅化反应应用
 2-苯基-2-（三甲硅氧基）丙腈
 
0.2mmol 配合物I, 苯甲醛0.1mL 及TMSCN 0.3 ml (3.3mmol), 2mL二氯甲烷 相继在20~30?C下加入，3天后， 加入水淬灭经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体, 产率为：83 %；1H NMR (300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1, 63.5, -0.39(x3)。

Claims (3)

1.一种手性锌氮配合物，其特征在于：由四腈乙烯和D-缬氨醇在无水无氧条件下和催化剂无水ZnCl2 其摩尔百分比是51mol%时于氯苯溶剂中回流反应72小时，由以下化学式（I）所示的配合物：
                                                                       
（Ⅰ）。
2.权利要求1所述的配合物(I)，在293k温度下，在牛津 X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线（λ=0.71073 A）以ω-θ 扫描方式收集衍射数据，其特征在于晶体属三斜晶系,空间群P3121，晶胞参数：a = 12.1660(10) ?，α= 90°； b = 12.1660(10) ?，β= 90°；c = 18.0515(19) ?，γ= 120°。
3.权利要求1所述的配合物(I)的合成方法，由四腈乙烯和D-缬氨醇在无水无氧条件下和催化剂无水ZnCl2 其摩尔百分比是51mol%时于氯苯溶剂中回流反应36小时分离、纯化，即反应结束后脱去氯苯，加水溶解后用氯仿萃取，萃取相脱溶后用柱层析纯化；将配合物（I）用二氯甲烷及甲醇（2:1）淋洗，柱层析分离，然后又加入正己烷、三氯甲烷、乙醇及四氢呋喃配置成饱和溶液，自然挥发后得配合物单晶。
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