CN103145742A - 一种手性噁唑啉锌配合物 - Google Patents
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- QXVWXKGGRMFBKI-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;zinc Chemical compound [Zn].C1CN=CO1 QXVWXKGGRMFBKI-UHFFFAOYSA-N 0.000 title claims abstract description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- JSOLVAGDJFHTHQ-UHFFFAOYSA-N piperidine;propanenitrile Chemical compound CCC#N.C1CCNCC1 JSOLVAGDJFHTHQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 3
- 239000011592 zinc chloride Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- NWYYWIJOWOLJNR-RXMQYKEDSA-N l-valinol Chemical compound CC(C)[C@H](N)CO NWYYWIJOWOLJNR-RXMQYKEDSA-N 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- -1 phenyl aldehyde Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- GUFGBPFTICJYDD-UHFFFAOYSA-L [Cl-].[Zn+2].O1C=NCC1.[Cl-] Chemical compound [Cl-].[Zn+2].O1C=NCC1.[Cl-] GUFGBPFTICJYDD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PBDJVYUVWSEUFK-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole zinc Chemical class [Zn].C1CN=CO1.C1CN=CO1 PBDJVYUVWSEUFK-UHFFFAOYSA-N 0.000 description 1
- NUHIGHWDCGKVGO-UHFFFAOYSA-N C1CN=CO1.C1CN=CO1.C1=CC=C2C3=CC=CC=C3NC2=C1 Chemical compound C1CN=CO1.C1CN=CO1.C1=CC=C2C3=CC=CC=C3NC2=C1 NUHIGHWDCGKVGO-UHFFFAOYSA-N 0.000 description 1
- 238000003489 Nozaki-Hiyama reaction Methods 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
- UHIJLWIHCPPKOP-UHFFFAOYSA-N [N].[Zn] Chemical compound [N].[Zn] UHIJLWIHCPPKOP-UHFFFAOYSA-N 0.000 description 1
- 238000006293 aldehyde allylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material 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
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 230000009466 transformation Effects 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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Abstract
一种手性噁唑啉锌配合物,其化学式如下:该配合物的合成方法,是由六氢吡啶丙腈39.7mmol和L-缬氨醇5.3192g在无水无氧条件下和催化剂无水ZnCl2236mol%于氯苯溶剂中回流反应60小时,然后分离、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,自然挥发第一组分点得配合物单晶。
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噁唑啉金属有机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。近年来手性锌噁唑啉金属配合物在不对称催化领域取得了较好的催化效果。
参考文献:
1.
New preparation of tridentate bis- oxazoline carbazole ligand effective
for enantioselective Nozaki-Hiyama reaction. Inoue, Masahiro; Nakada,
Masahisa.,Heterocycles (2007),
72 133-138.
2. Highly
enantioselective hetero Diels-Alder reactions of N-sulfinyl dienophiles
promoted by copper(II)- and zinc (II)-chiral bis( oxazoline )
complexes. Bayer, Annette; Gautun, Odd R.
Tetrahedron: Asymmetry (2001), 12(21), 2937-2939.
3. Bis(
oxazoline )-metal complexes immobilized by electrostatic
interactions as heterogeneous catalysts for enantioselective Diels-Alder
reactions.
Fraile, J. M.; Garcia, J. I.; Harmer, M. A.; Herrerias, C. I.; Mayoral, J. A.
Journal of Molecular Catalysis A: Chemical (2001), 165(1-2),
211-218.
4. Use of bis(
oxazoline )-metal complexes as chiral catalysts for asymmetric
Diels-Alder reactions using 2-acetyl-1,4-naphthoquione as a dienophile. Brimble,
Margaret A.; McEwan, John F. Sch. Chem., Univ.
Sydney, Sydney, Australia. Tetrahedron:
Asymmetry (1997), 8(24), 4069-4078.
5.
Enantioselective allylation of aldehydes promoted by chiral zinc
bis( oxazoline ) complexes. Cozzi, Pier
Giorgio; Orioli, Paolo; Tagliavini, Emilio; Umani-Ronchi, Achille. Tetrahedron
Letters (1997), 38(1), 145-148.
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邻遴选相应的原料并建立相应的方法合成手性催化剂。
本发明所称的手性锌氮配合物是六氢吡啶丙腈与L-缬氨醇在236mol% 氯化锌用一锅法制备的由以下化学式(I)所示的配合物:
(I)。
化学名称:4(S)-异丙基-2-甲基-4,5-二氢化噁唑啉氯化锌配合物,简称配合物(I)。
本手性配合物的合成方法包括反应、分离和纯化,其特征是由六氢吡啶丙腈39.7 mmol和L-缬氨醇5.3192g在无水无氧条件下和催化剂无水ZnCl2 236 mol% 于氯苯溶剂中回流反应60小时,然后分离、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)的合成方法是六氢吡啶丙腈和L-缬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,自然挥发第一组分点得配合物单晶。
该配合物在苯甲醛的腈硅化反应中显示一定的的催化性能,其转化率高达58%。
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
4
(
S
)
-
异丙基
-2-
甲基
-4,5-
二氢化噁唑啉氯化锌配合物的制备
100mL两口瓶中,无水无氧条件下,加入无水ZnCl2 5.4016g (39.7 mmol),
40mL氯苯, 六氢吡啶丙腈2.3215 g (16.8 mmol), L-缬氨醇 5.3192 g, 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(4:1)柱层析,得白色晶体,产率20%;元素分析C14H26Cl2N2O2Zn,理论值 :C: 43.49 %, H,6.71%, N, 7.17%;计算值:C:43.04%, H,7.19%, N,7.23
%;IR:3436,3284,3145,2954,2864,1725,1659,1585,1458, 1420,1393,1319,1278,1280,1219,1092,1038,974,952,905,765。
配合物晶体数据如下:
经验式
C14 H26Cl2 N2 O Zn
分子量
390.64
温度
140(2) K
波长
0.71073 A
晶系, 空间群 单斜晶系, P2(1)
晶胞参数
a = 6.494(2) A alpha = 90 deg.
b = 16.648(5)A beta = 109.082(5)deg
c = 9.129 (3) A gamma = 90 deg.
体积
932.6(5)A^3
电荷密度
2, 1.391 Mg/m^3
吸收
校正参数 1.608mm^-1
单胞内的电子数目 408
晶体大小
0.22x 0.16x 0.10mm
Theta 角的范围 2.36 to 30.59
HKL的指标收集范围
-8<=h<=9, -23<=k<20, -13<=l<=13
收集/独立衍射数据
8700/ 4982 [R(int) = 0.0456]
theta = 30.5的数据完整度 98.9 %
吸收校正的方法
多层扫描
最大最小的透过率
0.8558 and 0.7187
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
4982/1/196
精修使用的方法
0.992
衍射点的一致性因子
R1 = 0.0455,wR2= 0.1212
可观察衍射的吻合因子
R1 = 0.0551, wR2 = 0.1329
绝对构型参数
0.059(16)
差值傅里叶图上的最大峰顶和峰谷 1.060 and -0.716e.A^-3
晶体典型的键长数据:
Zn(1)-N(2)
2.033(3)
Zn(1)-N(1)
2.043(4)
Zn(1)-Cl(2)
2.2352(12)
Zn(1)-Cl(1)
2.2443(12)
N(1)-C(2)
1.274(6)
N(1)-C(4)
1.487(5)
N(2)-C(9)
1.274(5)
N(2)-C(11)
1.490(5)
O(1)-C(2)
1.343(5)
O(1)-C(3)
1.453(7)
O(2)-C(9)
1.341(5)
O(2)-C(10)
1.459(5)
晶体典型的键角数据:
N(2)-Zn(1)-N(1)
100.32(14)
N(2)-Zn(1)-Cl(2)
110.56(11)
N(1)-Zn(1)-Cl(2)
113.22(10)
N(2)-Zn(1)-Cl(1)
110.74(10)
N(1)-Zn(1)-Cl(1)
108.67(11)
Cl(2)-Zn(1)-Cl(1)
112.68(4)
C(2)-N(1)-C(4)
107.6(4)
C(2)-N(1)-Zn(1)
124.6(3)
C(4)-N(1)-Zn(1)
127.7(3)
C(9)-N(2)-C(11)
107.3(3)
C(9)-N(2)-Zn(1)
126.3(3)
C(11)-N(2)-Zn(1)
126.4(3)
C(2)-O(1)-C(3)
107.1(4)
C(9)-O(2)-C(10)
105.8(3)
(二)、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, TMSCN
0.3 ml (3.3mmol) 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:58 %。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)
2.权利要求1所述的配合物(I),在140(2)k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,其特征在于晶体属单斜晶系,空间群P 2(1),晶胞参数:a = 6.494(2) A alpha = 90 deg;
b = 16.648(5)A beta = 109.082(5)deg; c = 9.129 (3) A
gamma = 90 deg。
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,其特征是由六氢吡啶丙腈39.7 mmol和L-缬氨醇5.3192g在无水无氧条件下和催化剂无水ZnCl2 236 mol% 于氯苯溶剂中回流反应60小时,然后分离、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,自然挥发第一组分点得配合物单晶。
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CN106496254A (zh) * | 2016-10-18 | 2017-03-15 | 合肥祥晨化工有限公司 | 一种手性锌配合物 |
CN107935959A (zh) * | 2017-07-28 | 2018-04-20 | 合肥祥晨化工有限公司 | 一种手性化合物的合成方法及用途 |
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CN107935959A (zh) * | 2017-07-28 | 2018-04-20 | 合肥祥晨化工有限公司 | 一种手性化合物的合成方法及用途 |
CN107935959B (zh) * | 2017-07-28 | 2019-07-05 | 合肥祥晨化工有限公司 | 一种手性化合物的合成方法及用途 |
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