CN103232480B - 一种手性锌配合物 - Google Patents
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- 239000011701 zinc Substances 0.000 title abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract 7
- 229910052725 zinc Inorganic materials 0.000 title abstract 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims abstract description 7
- VPSSPAXIFBTOHY-LURJTMIESA-N (2s)-2-amino-4-methylpentan-1-ol Chemical compound CC(C)C[C@H](N)CO VPSSPAXIFBTOHY-LURJTMIESA-N 0.000 claims abstract description 6
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- UHIJLWIHCPPKOP-UHFFFAOYSA-N [N].[Zn] Chemical class [N].[Zn] UHIJLWIHCPPKOP-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 238000002447 crystallographic data Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005260 alpha ray Effects 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims 1
- 125000006850 spacer group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- 238000006842 Henry reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 6
- -1 Acyclic Alkenes Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- GBSQTQRZHMQHGH-UHFFFAOYSA-N 2-pyridin-2-yl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=N1 GBSQTQRZHMQHGH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PZVKSFBOPQYWGM-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;pyridine Chemical class C1CN=CO1.C1=CC=NC=C1 PZVKSFBOPQYWGM-UHFFFAOYSA-N 0.000 description 1
- FNUULAMKGYZPOZ-UHFFFAOYSA-N CC(CC1N)C1N Chemical compound CC(CC1N)C1N FNUULAMKGYZPOZ-UHFFFAOYSA-N 0.000 description 1
- 230000004568 DNA-binding Effects 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011982 enantioselective catalyst Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical class [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Abstract
一种手性锌配合物，其化学式如下：
Description
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.Enantioselective diene cyclization/hydrosilylation catalyzed by optically active palladiumbisoxazoline and pyridine-oxazoline complexes，Perch,Nicholas S.；Pei,Tao；Widenhoefer,Ross A.Journal of Organic Chemistry(2000),65(12),3836-3845.
2.Synthesis and evaluation of the in vitro DNA-binding properties of chiralcis-dichloro(pyridyloxazoline)platinum(II)complexes,Dodd,David W.；Toews,Heather E.；Trevail,Michael J.；Jennings,Michael C.；Hudson,Robert H.E.；Jones,Nathan D.,CanadianJournal of Chemistry(2009),87(1),321-327.
3.Asymmetric Intermolecular Heck-Type Reaction of Acyclic Alkenes via OxidativePalladium(II)Catalysis,Yoo,Kyung Soo；Park,Chan Pil；Yoon,Cheol Hwan；Sakaguchi,Satoshi；O'Neill,Justin；Jung,Kyung Woon,Organic Letters(2007),9(20),3933-3935。
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2-[4(S)-异丁基-4,5-二氢化]噁唑啉基吡啶锌配合物由邻氰基吡啶制备的由以下化学式所示的配合物：
化学名称：双{2-[4(S)-异丁基-4,5-二氢化]噁唑啉基吡啶}氯化锌配合物，简称配合物(I)。
本配合物(I)的合成方法包括反应、分离和纯化，其特征是由2-氰基吡啶2.0g和L-亮氨醇3.4g在无水无氧条件下和催化剂无水ZnCl2(126mol％)时于氯苯溶剂中回流反应60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2-氰基吡啶与L-亮氨醇在氯苯溶剂中回流反应60小时。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腈硅化反应中显示了较好的催化性能。
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)双{2-[4(S)-异丁基-4,5-二氢化]噁唑啉基吡啶}氯化锌配合物的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl23.3g(24.26mmol),40mL氯苯,2-氰基吡啶2.1279g(20.46mmol),L-亮氨醇3.3g,将混合物在高温下回流60h,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,将粗产品用石油醚/二氯甲烷(1:9)柱层析,得白色晶体，M.P.:>220℃，产率：35％；[a]5 D＝+32.1°(c＝0.062，CH3OH):,1HNMR(600MHz,CDCl3)8.70(s,1H,Ar-H),8.02～8.09(m,2H,Ar-H),7.72(s,1H,Ar-H),4.74(s,1H),4.22～4.24(m,2H),1.62～1.64(m,2H),1.31(d,J＝0.72Hz,1H),0.80～0.84(m,6H),13CNMR 23.2(x2),25.2(x2),27.8(x2),33.6(x2),44.5(x2),68.7(x2),124.1(x2),132.0(x2),139.5(x2),149.9(x2),163.5(x2)，IR:3413,3103，3077，2959,2934,2870,1774,1655,1594,1571,1492,1469,1405,1369,1300,1292,1259,1161,1089,1018,1048,938,804,756,707,683,640；元素分析：C:40.51％,H:5.10％,N:8.02％。
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Oxford X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线以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：
晶体典型的键长数据：
晶体的键角数据
(二)、亨利反应应用
1.(1E)-2-硝基乙烯基苯
催化剂I(0.15mmol),苯甲醛0.10mL(0.986mmol)及硝基甲烷(0.50mL,9.255mmol)在室温下搅拌120h，产率为：84.0％。1HNMR(300MHz,CDCl3),8.00(d,J＝23Hz,1H),7.47～7.63(m,6H)。
Claims (3)
1.一种手性锌配合物，其特征在于：由邻氰基吡啶和L-亮氨醇在无水无氧条件下和催化剂无水ZnCl2126mol％时于氯苯溶剂中回流反应60小时，由以下化学式(II)所示的配合物：
2.权利要求1所述的手性锌配合物，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射线以ω-θ扫描方式收集衍射数据，其特征在于晶体属斜方晶系,空间群C2，晶胞参数：α＝90°；β＝90°； γ＝90°。
3.由权利要求1所述的手性锌配合物的合成方法，由2-氰基吡啶和L-亮氨醇在无水无氧条件下和催化剂无水ZnCl2126mol％时于氯苯溶剂中回流反应60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；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。
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