CN106632426B - 一种手性锌配合物 - Google Patents
一种手性锌配合物 Download PDFInfo
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- UHIJLWIHCPPKOP-UHFFFAOYSA-N [N].[Zn] Chemical class [N].[Zn] UHIJLWIHCPPKOP-UHFFFAOYSA-N 0.000 title claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000010189 synthetic method Methods 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 238000002447 crystallographic data Methods 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VPSSPAXIFBTOHY-LURJTMIESA-N (2s)-2-amino-4-methylpentan-1-ol Chemical class CC(C)C[C@H](N)CO VPSSPAXIFBTOHY-LURJTMIESA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 5
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002825 nitriles Chemical class 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- -1 ammonia alcohols Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 235000013832 Valeriana officinalis Nutrition 0.000 abstract 1
- 244000126014 Valeriana officinalis Species 0.000 abstract 1
- 235000016788 valerian Nutrition 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 31
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012937 correction Methods 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
- 238000005712 Baylis-Hillman reaction Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002918 oxazolines Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 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
- 230000004568 DNA-binding Effects 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 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
- JHQXQMQQRHUMAT-UHFFFAOYSA-N [Zn].O1C(=NCC1)C1=NC=CC=C1 Chemical compound [Zn].O1C(=NCC1)C1=NC=CC=C1 JHQXQMQQRHUMAT-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000010668 complexation reaction 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis 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
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 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
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 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
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种手性锌配合物，其特征在于：其特征是由2‑氰基吡啶和L‑缬氨醇在无水无氧条件下和催化剂无水ZnCl2 65wt%时于氯苯溶剂中回流反应48小时，由以下化学式（I）所示的配合物：（I）。该配合物(I)的合成方法，是由2‑氰基吡啶和L‑亮氨醇在无水无氧条件下和催化剂无水ZnCl2(65wt%)时于氯苯溶剂中回流反应48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；将粗产品用石油醚/二氯甲烷按体积比为1:99柱层析,将第一组分点自然挥发，得白色晶体配合物；该配合物在苯甲醛的腈硅化反应、亨利反应及baylis‑hillman反应中显示较好的催化性能，其转化率分别为78%及99%及66%。
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 byoptically active palladium bisoxazoline and pyridine-oxazoline complexes ，Perch, Nicholas S.; Pei, Tao; Widenhoefer, Ross A. Journal of OrganicChemistry (2000), 65(12), 3836-3845.
2.Synthesis and evaluation of the in vitro DNA-binding properties ofchiral
cis-dichloro(pyridyloxazoline)platinum(II) complexes , Dodd, DavidW.; Toews, Heather E.; Trevail, Michael J.; Jennings, Michael C.; Hudson,Robert H. E.; Jones, Nathan D., Canadian Journal of Chemistry (2009), 87(1),321-327.
3.Asymmetric Intermolecular Heck-Type Reaction of Acyclic Alkenes viaOxidative Palladium(II) Catalysis ,Yoo, Kyung Soo; Park, Chan Pil; Yoon,Cheol Hwan; Sakaguchi, Satoshi; O'Neill, Justin; Jung, Kyung Woon, OrganicLetters (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2-[4(S)-异丁基-4,5-二氢化]噁唑啉基吡啶锌配合物，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-氰基吡啶和L-亮氨醇在无水无氧条件下和催化剂无水ZnCl2154wt% 时于氯苯溶剂中回流反应48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；将粗产品用石油醚/ 二氯甲烷按体积比为1:99柱层析, 将第一组分点自然挥发，得白色晶体配合物。
发明人在实验过程中，按石油醚/ 二氯甲烷体积比为1:9得到另一种晶体配合物，已申请专利，申请号为：201310029134.1。
该配合物在苯甲醛的腈硅化反应、亨利反应及baylis-hillman反应中显示较好的催化性能，其转化率分别为65%及99%及66%。
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）2-[4(S)-异丁基-4,5-二氢化]噁唑啉基吡啶锌配合物的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl2 3.2103 g , 40mL氯苯, 2-氰基吡啶2.0875g , L-亮氨醇3.6869 g, 将混合物在高温下回流48h,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/ 二氯甲烷按体积比为1:99柱层析, 将第一组分点自然挥发，得白色晶体, 熔点: 106-108°C, 产率58%；[a]5 D=+20.83º (c=0.288，CH3OH)：δH (600MHz, DMSO-d6, 27℃) 8.81 (d, J=4.8Hz, 1H), 8.19 (t, J=7.7Hz, 1H), 8.04 (d, J=7.8Hz, 1H), 7.84(t, J = 6.3Hz, 2H), 5.02 (t, J=9.1Hz, 1H), 4.58-4.63(m, 1H),4.49 (t, J=8.7Hz, 1H), 1.94-1.98 (m, 2H), 1.51-1.54 (m, 1H), 1.00-1.04(dd, J=6.3Hz, 6.2Hz, 6H);IR :3445, 3071，2957，2870, 1652, 1592, 1493, 1474, 1442,1404, 1389, 1298, 1280, 1160, 10921, 1050, 10198 941, 8033, 753, 664, 636,459; 元素分析C24H32Cl4N4O2Zn2：理论值：C: 42.32, H: 4.74, N: 8.23 %，实测值：C:42.51, H: 5.10, N: 8.02%。
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MoKa射线（λ=0.71073 A）以w-Theta 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 C24H32 Cl4 N4 O2 Zn2
分子量 681.07
温度 293(2) K
波长 0.71073 Å
晶系， 空间群 单斜晶系, P1
晶胞参数 a = 8.4425(15) Å α = 90 °.
b = 9.8894(17) Å β = 94.654(3) °.
c = 9.9721(17) Å γ= 90 °.
体积 759.9（2）Å^3
电荷密度 1, 1.488Mg/m^3
吸收 校正参数 1.957 mm^-1
单胞内的电子数目 348
晶体大小 0.200 x 0.160x 0.100 mm
Theta 角的范围 2.088 to 25.494
HKL的指标收集范围 -5<=h<=10, -11<=k<11, -12<=l<=11
收集/独立衍射数据 4370/ 3503[R(int) = 0.0163]
theta = 30.5的数据完整度 99.7 %
吸收校正的方法 多层扫描
最大最小的透过率 0.7456 and 0.6296
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 3503/4/329
精修使用的方法 1.017
衍射点的一致性因子 R1 = 0.0314，wR2= 0.0807
可观察衍射的吻合因子 R1 = 0.0369, wR2 = 0.0841
绝对构型参数 0.022（17）
差值傅里叶图上的最大峰顶和峰谷 0.388 and -0.182e.Å^-3
晶体典型的键长数据：
Zn(1)-N(1) 2.062(8)
Zn(1)-N(2) 2.118(7)
Zn(1)-Cl(1) 2.191(2)
Zn(1)-Cl(2) 2.200(2)
Zn(2)-N(3) 2.027(7)
Zn(2)-N(4) 2.133(6)
Zn(2)-Cl(3) 2.191(2)
Zn(2)-Cl(4) 2.204(2)
N(1)-C(6) 1.267(10)
N(1)-C(8) 1.473(11)
N(2)-C(1) 1.316(12)
N(2)-C(5) 1.381(12)
N(3)-C(18) 1.259(10)
N(3)-C(20) 1.488(10)
N(4)-C(17) 1.320(12)
N(4)-C(13) 1.335(13)
O(1)-C(6) 1.324(11)
O(1)-C(7) 1.477(12)
O(2)-C(18) 1.340(11)
O(2)-C(19) 1.465(12)
C(1)-C(2) 1.370(16)
C(1)-H(1) 0.9300
C(2)-C(3) 1.385(19)
C(2)-H(2) 0.9300
C(3)-C(4) 1.375(16)
C(3)-H(3) 0.9300
C(4)-C(5) 1.357(12)
C(4)-H(4) 0.9300
C(5)-C(6) 1.457(13)
C(7)-C(8) 1.497(12)
C(7)-H(7A) 0.9700
C(7)-H(7B) 0.9700
C(8)-C(9) 1.507(9)
C(8)-H(8) 0.9800
C(9)-C(10) 1.512(10)
C(9)-H(9A) 0.9700
C(9)-H(9B) 0.9700
C(10)-C(11) 1.519(10)
C(10)-C(12) 1.523(10)
C(10)-H(10) 0.9800
C(11)-H(11A) 0.9600
C(11)-H(11B) 0.9600
C(11)-H(11C) 0.9600
C(12)-H(12A) 0.9600
C(12)-H(12B) 0.9600
C(12)-H(12C) 0.9600
C(13)-C(14) 1.394(16)
C(13)-H(13) 0.9300
C(14)-C(15) 1.333(18)
C(14)-H(14) 0.9300
C(15)-C(16) 1.372(16)
C(15)-H(15) 0.9300
C(16)-C(17) 1.370(11)
C(16)-H(16) 0.9300
C(17)-C(18) 1.475(12)
C(19)-C(20) 1.529(12)
C(19)-H(19A) 0.9700
C(19)-H(19B) 0.9700
C(20)-C(21) 1.485(10)
C(20)-H(20) 0.9800
C(21)-C(22) 1.525(10)
C(21)-H(21A) 0.9700
C(21)-H(21B) 0.9700
C(22)-C(23) 1.464(12)
C(22)-C(24) 1.521(12)
C(22)-H(22) 0.9800
C(23)-H(23A) 0.9600
C(23)-H(23B) 0.9600
C(23)-H(23C) 0.9600
C(24)-H(24A) 0.9600
C(24)-H(24B) 0.9600
C(24)-H(24C) 0.9600
晶体的键角数据
N(1)-Zn(1)-N(2) 80.3(3)
N(1)-Zn(1)-Cl(1) 114.41(19)
N(2)-Zn(1)-Cl(1) 111.6(2)
N(1)-Zn(1)-Cl(2) 115.43(19)
N(2)-Zn(1)-Cl(2) 107.2(2)
Cl(1)-Zn(1)-Cl(2) 120.29(10)
N(3)-Zn(2)-N(4) 79.5(3)
N(3)-Zn(2)-Cl(3) 116.65(19)
N(4)-Zn(2)-Cl(3) 108.67(19)
N(3)-Zn(2)-Cl(4) 110.41(18)
N(4)-Zn(2)-Cl(4) 113.53(19)
Cl(3)-Zn(2)-Cl(4) 120.78(10)
C(6)-N(1)-C(8) 107.9(7)
C(6)-N(1)-Zn(1) 111.7(6)
C(8)-N(1)-Zn(1) 140.4(5)
C(1)-N(2)-C(5) 118.1(9)
C(1)-N(2)-Zn(1) 130.4(8)
C(5)-N(2)-Zn(1) 111.4(6)
C(18)-N(3)-C(20) 107.9(7)
C(18)-N(3)-Zn(2) 113.1(6)
C(20)-N(3)-Zn(2) 139.0(5)
C(17)-N(4)-C(13) 118.5(8)
C(17)-N(4)-Zn(2) 112.4(6)
C(13)-N(4)-Zn(2) 128.9(8)
C(6)-O(1)-C(7) 105.6(6)
C(18)-O(2)-C(19) 103.9(6)
N(2)-C(1)-C(2) 122.2(12)
N(2)-C(1)-H(1) 118.9
C(2)-C(1)-H(1) 118.9
C(1)-C(2)-C(3) 120.8(11)
C(1)-C(2)-H(2) 119.6
C(3)-C(2)-H(2) 119.6
C(4)-C(3)-C(2) 116.7(10)
C(4)-C(3)-H(3) 121.7
C(2)-C(3)-H(3) 121.7
C(5)-C(4)-C(3) 120.9(12)
C(5)-C(4)-H(4) 119.5
C(3)-C(4)-H(4) 119.5
C(4)-C(5)-N(2) 121.3(9)
C(4)-C(5)-C(6) 125.9(10)
N(2)-C(5)-C(6) 112.5(7)
N(1)-C(6)-O(1) 117.6(8)
N(1)-C(6)-C(5) 123.5(8)
O(1)-C(6)-C(5) 118.8(7)
O(1)-C(7)-C(8) 104.4(8)
O(1)-C(7)-H(7A) 110.9
C(8)-C(7)-H(7A) 110.9
O(1)-C(7)-H(7B) 110.9
C(8)-C(7)-H(7B) 110.9
H(7A)-C(7)-H(7B) 108.9
N(1)-C(8)-C(7) 103.3(8)
N(1)-C(8)-C(9) 113.2(7)
C(7)-C(8)-C(9) 113.6(8)
N(1)-C(8)-H(8) 108.8
C(7)-C(8)-H(8) 108.8
C(9)-C(8)-H(8) 108.8
C(8)-C(9)-C(10) 114.8(5)
C(8)-C(9)-H(9A) 108.6
C(10)-C(9)-H(9A) 108.6
C(8)-C(9)-H(9B) 108.6
C(10)-C(9)-H(9B) 108.6
H(9A)-C(9)-H(9B) 107.5
C(9)-C(10)-C(11) 114.4(7)
C(9)-C(10)-C(12) 108.5(8)
C(11)-C(10)-C(12) 107.6(7)
C(9)-C(10)-H(10) 108.7
C(11)-C(10)-H(10) 108.7
C(12)-C(10)-H(10) 108.7
C(10)-C(11)-H(11A) 109.5
C(10)-C(11)-H(11B) 109.5
H(11A)-C(11)-H(11B) 109.5
C(10)-C(11)-H(11C) 109.5
H(11A)-C(11)-H(11C) 109.5
H(11B)-C(11)-H(11C) 109.5
C(10)-C(12)-H(12A) 109.5
C(10)-C(12)-H(12B) 109.5
H(12A)-C(12)-H(12B) 109.5
C(10)-C(12)-H(12C) 109.5
H(12A)-C(12)-H(12C) 109.5
H(12B)-C(12)-H(12C) 109.5
N(4)-C(13)-C(14) 120.7(12)
N(4)-C(13)-H(13) 119.7
C(14)-C(13)-H(13) 119.7
C(15)-C(14)-C(13) 119.5(10)
C(15)-C(14)-H(14) 120.2
C(13)-C(14)-H(14) 120.2
C(14)-C(15)-C(16) 120.4(10)
C(14)-C(15)-H(15) 119.8
C(16)-C(15)-H(15) 119.8
C(17)-C(16)-C(15) 117.4(11)
C(17)-C(16)-H(16) 121.3
C(15)-C(16)-H(16) 121.3
N(4)-C(17)-C(16) 123.4(9)
N(4)-C(17)-C(18) 112.7(7)
C(16)-C(17)-C(18) 123.8(10)
N(3)-C(18)-O(2) 119.3(8)
N(3)-C(18)-C(17) 122.2(8)
O(2)-C(18)-C(17) 118.4(7)
O(2)-C(19)-C(20) 105.7(8)
O(2)-C(19)-H(19A) 110.6
C(20)-C(19)-H(19A) 110.6
O(2)-C(19)-H(19B) 110.6
C(20)-C(19)-H(19B) 110.6
H(19A)-C(19)-H(19B) 108.7
C(21)-C(20)-N(3) 112.9(6)
C(21)-C(20)-C(19) 115.1(7)
N(3)-C(20)-C(19) 101.5(7)
C(21)-C(20)-H(20) 109.0
N(3)-C(20)-H(20) 109.0
C(19)-C(20)-H(20) 109.0
C(20)-C(21)-C(22) 116.5(6)
C(20)-C(21)-H(21A) 108.2
C(22)-C(21)-H(21A) 108.2
C(20)-C(21)-H(21B) 108.2
C(22)-C(21)-H(21B) 108.2
H(21A)-C(21)-H(21B) 107.3
C(23)-C(22)-C(24) 110.4(8)
C(23)-C(22)-C(21) 113.8(7)
C(24)-C(22)-C(21) 111.7(8)
C(23)-C(22)-H(22) 106.9
C(24)-C(22)-H(22) 106.9
C(21)-C(22)-H(22) 106.9
C(22)-C(23)-H(23A) 109.5
C(22)-C(23)-H(23B) 109.5
H(23A)-C(23)-H(23B) 109.5
C(22)-C(23)-H(23C) 109.5
H(23A)-C(23)-H(23C) 109.5
H(23B)-C(23)-H(23C) 109.5
C(22)-C(24)-H(24A) 109.5
C(22)-C(24)-H(24B) 109.5
H(24A)-C(24)-H(24B) 109.5
C(22)-C(24)-H(24C) 109.5
H(24A)-C(24)-H(24C) 109.5
H(24B)-C(24)-H(24C) 109.5
腈硅化反应应用
2-苯基-2-（三甲硅氧基）丙腈
0.20mmol 配合物I, 苯甲醛0.1mL, TMSCN 0.3 ml (3.3mmol), 2mL二氯甲烷 相继在20~30˚C下加入，60h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：78%；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)。
亨利反应应用
取0.20mmol的配合物I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，室温搅拌，反应60小时后，进行核磁分析，转化率：>99%；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)。
Baylis-Hillman反应应用
取0.10mmol的配合物I（催化用量为10％）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：66%; 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)。
Claims (3)
1.一种手性锌配合物，其化学式(I)如下：
2.权利要求1所述的配合物(I)，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MoKa射线以ω-θ扫描方式收集衍射数据，其特征在于晶体属单斜晶系,空间群P1，晶胞参数： α＝90°；β＝94.654(3)°；γ＝90°。
3.权利要求1所述的配合物(I)的合成方法，包括反应、分离和纯化，其特征是由2-氰基吡啶和L-亮氨醇在无水无氧条件下和催化剂无水ZnCl2 154wt％时于氯苯溶剂中回流反应48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；将粗产品用石油醚/二氯甲烷按体积比为1:99柱层析,将第一组分点自然挥发，得白色晶体配合物。
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