CN102336776B - Chiral zinc nitrogen complex - Google Patents

Abstract

The invention provides a chiral zinc nitrogen complex, which is a 2(S)-{4S-isopropyl-2-[2-(4S-isopropyl-4,5-dihydro-2-oxazolines)-phenyl]-4,5,-dihydro-1-oxazolines}-3-methyl-1-butanol zinc chloride complex, and is characterized in that the complex shown in the following chemical formula is prepared by 1,2-di-nitrile-benzene, L-valinol and a catalyst anhydrous zinc chloride under water-free and oxygen-free conditions. The synthetic method of the complex comprises the following steps: reflux-reacting 1,2-di-nitrile-benzene, L-valinol and a catalyst anhydrous ZnCl2 (40-50 mol%) under water-free and oxygen-free conditions in a chlorobenzene solvent for 24 hours, then separating, purifying, removing chlorobenzene after finishing the reaction, adding water for dissolving, extracting by using chloroform, precipitating the extract phase and purifying by using column chromatography; leaching the complex (I) by using petroleum ether and dichloromethane, separating by column chromatography, naturally volatilizing to obtain complex monocrystal. The complex displays good catalytic property in nitrile silicification reaction of 2-methyl benzaldehyde, and conversion rate thereof is as high as 96%.

Description

A kind of chirality zinc-nitrogen coordination compound

One, technical field

The present invention relates to a kind of organometallic complex (title complex) and preparation method thereof, particularly nitrogenous chiral metal organic coordination compound and preparation method thereof, be exactly a kind of chiral oxazoline a metal-organic complex and synthetic method thereof.

Two, background technology

Along with vitochemical development, the application of organometallics in organic synthesis is more and more wide, is one of field very active in present organic chemistry, is widely used in organic synthesis.The use chiral ligand that the later stage sixties 20th century occurs and the asymmetric catalysis synthesis of transition metal complex catalysis have accelerated the research of chiral drug greatly.The important content of chemical catalysis dissymmetric synthesis is the design [1-9] of chiral ligand and containing metal catalyzer, thereby makes reaction have efficient and high enantioselectivity.Shou Xin oxazoline, tetrahydroglyoxaline metal complexes have been obtained catalytic effect preferably in asymmetric catalysis field in recent years.【10-13】

Reference:

1.Coordination properties of zinc 5，15-di(o-aminophenyl)octaalkylporphyrin in reactions with mono-and dibasic nitrogen bases.Zaitseva，S.V.；Zdanovitch，S.A.；Koifman，O.I.Russian Journal of Inorganic Chemistry(2010)，55(10)，1574-1580.

2.Three zinc(II)complexes constructed from aromatic dicarboxylate and1，4-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene：Syntheses，crystal structures and luminescent properties.Liu，Guang-Xiang；Xu，Yu-Yong；Wang，Yan；Nishihara，Sadafumi；Ren，Xiao-Ming.Inorganica Chimica Acta(2010)，363(14)，3932-3938.

3.Synthesis，structures，and properties of zinc(II)and cadmium(II)complexes with1，2，4，5-tetrakis(imidazol-1-ylmethyl)benzene and multicarboxylate ligands.Hua，Qin；Zhao，Yue；Xu，Guan-Cheng；Chen，Man-Sheng；Su，Zhi；Cai，Kai；Sun，Wei-Yin.Crystal Growth & Design(2010)，10(6)，2553-2562.

4.Metal carboxylate-phosphonates containing flexible N-donor co-ligands.Wang，Peng-Fei；Duan，Yan；Cao，Deng-Ke；Li，Yi-Zhi；Zheng，Li-Min.Dalton Transactions(2010)，39(19)，4559-4565.

5.Synthesis，crystal structure and properties of Zn(II)and Cd(II)complexes with2-(4-isopropyl-4-methyl-5-oxo-4，5-dihydro-1H-imidazol-2-yl)nicotinic acid ligand.Hu，Fei-Long；Yin，Xian-Hong；Mi，Yan；Zhang，Shan-Shan；Luo，Wei-Qiang；Zhuang，Yue.Inorganic Chemistry Communications(2010)，13(1)，33-36.

6.Biomimetic zinc(II)and cobalt(II)complexes with tri-tert-butoxysilanethiolate and imidazole ligands-Structural and spectroscopic studies.Dolega，Anna；Pladzyk，Agnieszka；Baranowska，Katarzyna；Jezierska，Julia.Inorganica Chimica Acta(2009)，362(14)，5085-5096.

7.Syntheses，Structures，and Fluorescent Properties of 2-(1H-Imidazol-2-yl)phenols and Their Neutral Zn(II)Complexes.Eseola，Abiodun Omokehinde；Li，Wen；Gao，Rong；Zhang，Min；Hao，Xiang；Liang，Tongling；Obi-Egbedi，Nelson Okpako；Sun，Wen-Hua.Inorganic Chemistry(Washington，DC，United States)(2009)，48(19)，9133-9146.

8.New preparation of tridentate bis-oxazoline carbazole ligand effective for enantioselective Nozaki-Hiyama reaction.Inoue，Masahiro；Nakada，Masahisa.，Heterocycles(2007)，72 133-138.

9.Syntheses，Structures，and Luminescent Properties of Zinc(II)and Cadmium(II)Coordination Complexes Based on Different(Pyridyl)imidazole Derivatives and 1，4-Benzenedicarboxylate.Lan，Ya-Qian；Li，Shun-Li；Fu，Yao-Mei；Du，Dong-Ying；Zang，Hong-Ying；Shao，Kui-Zhan；Su，Zhong-Min；Fu，Qiang.Crystal Growth & Design(2009)，9(3)，1353-1360.

10.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.

11.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.

12.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.

13.Enantioselective allylatlon 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.

Three, summary of the invention

The present invention aims to provide a kind of Zn-N a metal-organic complex to be applied to catalytic field, and technical problem to be solved is selected the neighbour and selected corresponding raw material and set up corresponding method synthesis of chiral catalyzer.

The alleged chirality zinc-nitrogen coordination compound of the present invention is by the title complex shown in following chemical formula (I):

Chemical name: 2 (S)-and 4S-sec.-propyl-2-[2-(4S-sec.-propyl-4,5-dihydro-2-oxazolinyl)-phenyl]-4,5 ,-dihydro-1-imidazolinyl }-3-methyl-1-butanol zinc chloride title complex, be called for short title complex (I).

The synthetic method of this chiral coordination compound adopts one kettle way to comprise reaction, separation and purifying, it is characterized in that by 1,2-dinitrile benzene and L-valerian ammonia alcohol under the anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer ₂(40-50mol%) back flow reaction 24 hours in chlorobenzene solvent, then separate, purifying, i.e. reaction is sloughed chlorobenzene after finishing, and the rear chloroform extraction of using that is dissolved in water, use column chromatography purification after the extraction phase precipitation;

The synthetic method of this chiral coordination compound (I) is 1,2-dinitrile benzene and L-valerian ammonia alcohol back flow reaction 24 hours in chlorobenzene solvent.

Sherwood oil and eluent methylene chloride for title complex (I), column chromatography for separation, volatilization one step get Han oxazoline and tetrahydroglyoxaline zinc chloride complex monocrystal naturally.

This title complex (I) shows catalytic performance preferably in the nitrile silicification reaction of 2-tolyl aldehyde, and its transformation efficiency reaches 96%.

Four, accompanying drawing explanation

Fig. 1 is the single crystal diffraction figure of title complex (I).

Five, embodiment

(1) preparation of chiral coordination compound (I)

In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl ₂4.0g (29.4mmol), the 40mL chlorobenzene, 1,2-dinitrile benzene 6.7g (56.7mmol), L-valerian ammonia alcohol 16g, by the mixture 24h that at high temperature refluxes, stopped reaction, decompression is with except desolventizing,, by the residuum water dissolution, and use CHCl ₃(20mLx2) extraction, the organic phase anhydrous sodium sulfate drying, rotation removes desolventizing, by thick sherwood oil/methylene dichloride (1: 4) column chromatography for product, obtains white crystal, productive rate 30%; [a] ⁵ _d=+34.4 ° of (c=0.0436, CH ₃cl): ultimate analysis C ₂₃h ₃₅n ₃cl ₂o ₂zn:C, 53.55%; H, 6.87%; N, 7.78%; Calculated value: C:52.94%; H, 6.76%; N, 8.05%; IR:3436,2961,2923,2874,1635,1604,1571,1520,1464,1377,1317,1300,1138,1074,1047,1026,946,784,766.

(2), nitrile silicification reaction application

0.20mmol title complex (I), 2-tolyl aldehyde 0.1mL, TMSCN 0.3ml (3.3mmol) adds in succession under 20～30 ℃, after 3d, adds the shrend (sherwood oil/methylene dichloride: 5/1), obtain colourless oil liquid after the post layer that goes out.Transformation efficiency: 96%, ¹h NMR (300MHz, CDCl ₃) 7.52-7.53 (d, 7.5Hz, 1H), 7.20-7.30 (m, 3H), 5.57 (s, 1H), 2.44 (s, 3H), 022 (s, 9H). ¹³c NMR (75MHz, CDCl ₃) 135.8,134.2,131.2,129.5,127.1,126.6,118.9,62.1,18.9 ,-0.2 (X3).

Claims (2)

1. a chirality zinc-nitrogen coordination compound, be a kind of 2 (S)-{ 4S-sec.-propyl-2-[2-(4S-sec.-propyl-4,5-dihydro-2-oxazolinyl)-phenyl]-4,5-dihydro-1-imidazolinyl }-3-methyl-1-butanol zinc chloride title complex, it is characterized in that by 1,2-dinitrile benzene and L-valerian ammonia alcohol under the anhydrous and oxygen-free condition and prepared by the catalyzer Zinc Chloride Anhydrous.

2. the synthetic method of chirality zinc-nitrogen coordination compound claimed in claim 1, by 1,2-dinitrile aniline and L-valerian ammonia alcohol under the anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer ₂40-50mol% back flow reaction 24 hours in chlorobenzene solvent, then separate, purifying, i.e. reaction is sloughed chlorobenzene after finishing, and the rear chloroform extraction of using that is dissolved in water, use column chromatography purification after the extraction phase precipitation; Sherwood oil and eluent methylene chloride for title complex, column chromatography for separation, complex monocrystal naturally volatilizees to obtain.

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