CN101392006A - 轴手性含双席夫碱双膦配体 - Google Patents
轴手性含双席夫碱双膦配体 Download PDFInfo
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- CN101392006A CN101392006A CNA2008102022936A CN200810202293A CN101392006A CN 101392006 A CN101392006 A CN 101392006A CN A2008102022936 A CNA2008102022936 A CN A2008102022936A CN 200810202293 A CN200810202293 A CN 200810202293A CN 101392006 A CN101392006 A CN 101392006A
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- 239000003446 ligand Substances 0.000 title claims abstract description 21
- 239000002262 Schiff base Substances 0.000 title claims abstract description 14
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006735 epoxidation reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 3
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 2
- 150000004753 Schiff bases Chemical class 0.000 abstract 1
- 238000005888 cyclopropanation reaction Methods 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- ONQRMOMMIPJWKD-UHFFFAOYSA-N [N].[N].P Chemical group [N].[N].P ONQRMOMMIPJWKD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明涉及一种化工技术领域的轴手性含双席夫碱双膦配体，结构式如下所示。本发明含有联苯类的轴手性，可应用于各种金属催化的不对称反应中，如烯烃的不对称环氧化反应，不对称环丙烷化反应等等，具有较高的反应活性(可达到70％以上)和立体选择性(可达到80％以上)。
Description
技术领域
本发明涉及一种化工技术领域的化合物，具体的说，涉及一种轴手性含双席夫碱双膦配体。
背景技术
手性配体是不对称催化产生不对称诱导和控制的源泉，优秀的手性配体不仅能有效调节活性金属中心的电子性能，而且能在金属中心周围构筑特异的手性微环境。C2型轴手性双膦配体，由于其结构的特殊性，被广泛应用于金属催化的各类不对称反应中。经过30年来的发展，已有大量的双膦配体涌现出来。经多年的研究积累含有联萘结构的轴手性双膦配体BINAP已成功地应用于工业化生产具有光学活性的化合物上。从BINAP出现时，科学家们就致力于获得既能拥有良好不对称反应性、选择性，又能通过更简便的方法来合成的配体。
经对现有技术的文献检索发现，Antonio Mezzetti在《Organometallics》(有机金属)2000，pp.4117-4126上发表的“Ruthenium(II)Complexeswith Chiral Tetradentate P2N2 Ligands Catalyze the Asymmetric Epoxidationof Olefins with H2O2”(钌的四配位双膦双氮配体在双氧水作用下催化烯烃环氧化反应中的应用。)，该文中提出的轴手性含双席夫碱双膦配体在不对称环氧化反应中取得了较好的反应活性及对映选择性。但该文中提出的轴手性含双席夫碱配体的联芳基轴邻位基团是甲基，甲基的位阻较大，限制了联苯可转动的角度，即限制了二面角。而二面角的大小已被证实影响着不对称催化反应的催化活性和选择性。为此设计新型的轴手性含双席夫碱双膦配体，研究其联芳基轴二面角大小对不对称催化反应的影响具有重要的学术和现实意义。
发明内容
本发明的目的在于针对现有技术的不足，提供一种轴手性含双席夫碱双膦配体，可以应用于不对称催化反应得到较高的反应活性和立体选择性。
本发明是通过以下技术方案实现的，本发明提供一种轴手性含双席夫碱双膦配体I，该配体的结构式如下：
该配体是轴具有(R)或(S)构型的对映异构体化合物，其结构式分别如下II、III：
本发明上述轴手性含双席夫碱双膦配体，其合成方法是：以(R)或(S)构型的光学纯6，6’-二甲氧基-2，2’-联苯二胺为原料和2-二苯基膦苯甲醛反应分别得到(R)或(S)构型的光学纯目标化合物II和III。
本发明上述轴具有(R)构型的化合物IV的结构式为：
轴具有(S)构型的化合物V的结构式为：
本发明含有联苯类的轴手性，可应用于各种金属催化的不对称反应中，如烯烃的不对称环氧化反应，不对称环丙烷化反应等等，具有较高的反应活性(可达到70％以上)和立体选择性(可达到80％以上)。
具体实施方式
下面对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
(1)从化合物IV制备化合物II
将化合物IV(1.0g，4.1mmol)和2-二苯基膦苯甲醛(2.38g，8.2mmol)一起在甲苯中回流反应十四个小时，蒸发除去溶剂后用柱层析纯化得产物II(2.9g，89％)。
1H NMR(CDCl3400，MHz)δ 8.93(d，2H，N＝CH，J＝5.6Hz)，7.78-6.69(m，32H，ArH)，6.35(d，2H，ArH)，3.82(s，6H，OCH3)31P NMR(CDCl3，161MHz)δ-14.17
实施例2
(1)从化合物V制备化合物III
将化合物V(2.0g，8.2mmol)和2-二苯基膦苯甲醛(4.76g，16.4mmol)一起在甲苯中回流反应十四个小时，蒸发除去溶剂后用柱层析纯化得产物III(5.7g，87％)。
1H NMR(CDCl3400，MHz)δ 8.93(d，2H，N＝CH，J＝5.6Hz)，7.78-6.69(m，32H，ArH)，6.35(d，2H，ArH)，3.82(s，6H，OCH3)31P NMR(CDCl3，161MHz)δ-14.18
该实施例合成方法简单，收率可达到89％以上。所制备的轴手性含双席夫碱双膦配体可与钌等金属离子配位催化如烯烃的不对称环氧化反应、不对称环丙烷化反应等。
Claims (2)
1.一种轴手性含双席夫碱双膦配体，其特征在于，结构式如下：
2.如权利要求1所述的轴手性含双席夫碱双膦配体，其特征是，所述的含双席夫碱双膦配体是轴具有(R)和(S)构型的对映异构体化合物，其结构式如下：
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| CNA2008102022936A CN101392006A (zh) | 2008-11-06 | 2008-11-06 | 轴手性含双席夫碱双膦配体 |
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| CNA2008102022936A CN101392006A (zh) | 2008-11-06 | 2008-11-06 | 轴手性含双席夫碱双膦配体 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093420A (zh) * | 2010-12-08 | 2011-06-15 | 厦门大学 | 手性大环胺膦配体及其制备方法和应用 |
| CN103554183A (zh) * | 2013-09-11 | 2014-02-05 | 南开大学 | 一种新型多芳基桥联的长链二膦配体合成方法和应用 |
| US10556886B2 (en) | 2016-07-29 | 2020-02-11 | Lg Chem, Ltd. | Metal-organic hybrid structures built with multi-directional polydentate ligands |
| US10562845B2 (en) | 2016-07-29 | 2020-02-18 | Lg Chem, Ltd. | Multi-directional polydentate ligands for metal-organic hybrid structures |
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2008
- 2008-11-06 CN CNA2008102022936A patent/CN101392006A/zh active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093420A (zh) * | 2010-12-08 | 2011-06-15 | 厦门大学 | 手性大环胺膦配体及其制备方法和应用 |
| CN102093420B (zh) * | 2010-12-08 | 2013-04-17 | 厦门大学 | 手性大环胺膦配体及其制备方法和应用 |
| CN103554183A (zh) * | 2013-09-11 | 2014-02-05 | 南开大学 | 一种新型多芳基桥联的长链二膦配体合成方法和应用 |
| US10556886B2 (en) | 2016-07-29 | 2020-02-11 | Lg Chem, Ltd. | Metal-organic hybrid structures built with multi-directional polydentate ligands |
| US10562845B2 (en) | 2016-07-29 | 2020-02-18 | Lg Chem, Ltd. | Multi-directional polydentate ligands for metal-organic hybrid structures |
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Open date: 20090325 |