CN102850383B - A kind of chiral zinc nitrogen complexes - Google Patents
A kind of chiral zinc nitrogen complexes Download PDFInfo
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- CN102850383B CN102850383B CN201210320992.7A CN201210320992A CN102850383B CN 102850383 B CN102850383 B CN 102850383B CN 201210320992 A CN201210320992 A CN 201210320992A CN 102850383 B CN102850383 B CN 102850383B
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Abstract
A kind of chirality zinc-nitrogen coordination compound, its chemical formula is as follows:
the synthetic method of this title complex by four nitrile ethene and D-valerian ammonia alcohol under anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer
2(42%) time in chlorobenzene solvent back flow reaction 36 hours be separated, purifying, namely reaction sloughs chlorobenzene after terminating, with chloroform extraction after being dissolved in water, with column chromatography purification after extraction phase precipitation; By title complex (I) sherwood oil and eluent methylene chloride, column chromatography for separation, volatilize to obtain complex monocrystal naturally.This title complex shows certain catalytic performance in the allyl group alkylated reaction of phenyl aldehyde, Baylis-Hillman reaction, Henle reaction and silicon cyanation, and its transformation efficiency reaches 32% respectively, and 27%, 50%, 68%.
Description
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, is exactly a kind of chirality zinc-nitrogen coordination compound 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 of very enlivening in present organic chemistry, has been widely used in organic synthesis.The asymmetric catalysis synthesis of the use chiral ligand that the later stage sixties 20th century occurs and transition metal complex catalysis accelerates the research of chiral drug greatly.The important content of chemical catalysis dissymmetric synthesis is the design of chiral ligand and containing metal catalyzer, thus makes reaction have efficient and high enantioselectivity.The part Shi oxazoline that usual asymmetric catalyst is used, Jin Lai oxazoline Zn complex is extensively synthesized and is obtained good catalytic effect.
Reference:
1.Synthesisofhighlymodularbis(oxazoline)ligandsbySuzukicross-couplingandevaluationascatalyticligands，Cattoen,Xavier；Pericas,MiquelA.Tetrahedron，65(39)，8199-8205.
2.Thesynthesisofnewoxazoline-containingbifunctionalcatalystsandtheirapplicationintheadditionofdiethylzinctoaldehydes,Coeffard,Vincent；Mueller-Bunz,Helge；Guiry,PatrickJ,Organic&BiomolecularChemistry,7(8),1723-1734.
3.NewBis(oxazolinyl)phenyl-Ruthenium(II)ComplexesandTheirCatalyticActivityforEnantioselectiveHydrogenationandTransferHydrogenationofKetones,Ito,Jun-ichi；Ujiie,Satoshi；Nishiyama,Hisao,Organometallics,28(2),630-638.
4.LewisAcid-CatalyzedEnantioselectiveHydroxylationReactionsofOxindolesandβ-KetoEstersUsingDBFOXLigand，Ishimaru,Takehisa；Shibata,Norio；Nagai,Jun；Nakamura,Shuichi；Toru,Takeshi；Kanemasa,Shuji,JournaloftheAmericanChemicalSociety，128(51),6488-16489。
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 Lin Xuan oxazoline to be solved is as part and synthesis of chiral zinc-nitrogen coordination compound.
Chiral zinc nitrogen complexes alleged by the present invention be two-(4-sec.-propyl-4,5-dihydro-2-oxazolinyl)-acetonitrile Zn complex by four nitrile ethylene making by the title complex shown in following chemical formula:
Chemical name: two-(4-sec.-propyl-4,5-dihydro-2-oxazolinyl)-acetonitrile Zn complex, is called for short title complex (I).
The synthetic method of this chipal compounds comprises reaction, abstraction and purification, the reaction that it is characterized in that preparing intermediate by four nitrile ethene and D-valerian ammonia alcohol under anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer
2(47%) time in chlorobenzene solvent back flow reaction 36 hours be separated, purifying, namely reaction sloughs chlorobenzene after terminating, with chloroform extraction after being dissolved in water, with column chromatography purification after extraction phase precipitation;
The synthetic method of this title complex (I) is four nitrile ethene and D-valerian ammonia alcohol back flow reaction 36 hours in chlorobenzene solvent.
Title complex (I) sherwood oil and eluent methylene chloride, column chromatography for separation, volatilize to obtain complex monocrystal naturally.
The reaction mechanism of this title complex can be speculated as four nitrile ethene in atmosphere and under zinc chloride effect, unstable, resolves into three itrile group methane, with the D-valerian ammonia alcohol effect of 2 molecules formed bisoxazoline again with zinc chloride according to 2:1 coordination, and slough two molecule hydrochloric acid.
Four, accompanying drawing explanation
Fig. 1 is the single crystal diffraction figure of title complex (I).
Five, embodiment
(1) preparation of chiral coordination compound
1, the preparation of two-(4-sec.-propyl-4,5-dihydro-2-oxazolinyl)-acetonitrile Zn complex
In 100mL two-mouth bottle, under anhydrous and oxygen-free condition, add anhydrous ZnCl
20.45g (3.30mmol), 40mL chlorobenzene, four nitrile ethene 1.0g (7.81mmol), D-valerian ammonia alcohol 4g, at high temperature reflux mixture 24h, stopped reaction, reduces pressure to remove desolventizing, by residuum water dissolution, and use
CHCl
3(20mLx2) extract, organic phase anhydrous sodium sulfate drying, rotate except desolventizing, by thick product sherwood oil/methylene dichloride (4:1) column chromatography, obtain white crystal, productive rate 52%; [a]
5 d=+306.6 ° of (c=0.20, CH
2cl
2):
1hNMR (500MHz, CDCl
3, 27 DEG C), δ (ppm)=4.35 (t, 4H), 4.16 (t, J=1Hz, 4H), 3.81 ~ 3.83 (m, 4H), 1.62 ~ 1.66 (m, 4H), 0.74 ~ 0.87 (dd, J=7Hz, 6.5Hz, 24H);
13cNMR (75MHz, CDCl
3) 170.6 (x2), 118.6 (x2), 73.0 (x4), 68.9 (x4), 68.5 (x4), 31.8 (x4), 19.2 (x4), 15.7 (x4).IR:3443 (s), 2963 (s), 2200 (s), 1609 (s), 1533 (s), 1484 (s), 1432 (s), 1391 (m), 1371 (w), 1341 (w), 1312 (w), 1251 (m), 1222 (m), 1117 (m), 1075 (s), 953 (m), 744 (m), 566 (w), 528 (w), 457 (w); Ultimate analysis: C:56.80%, H, 6.79%, N, 14.35%.
The crystal structure determination of compound:
The monocrystalline choosing suitable size under the microscope at room temperature carries out the experiment of X-ray single crystal diffraction, at 293k temperature, on the X-ray single crystal diffraction instrument of Oxford, with the MoK alpha-ray through graphite monochromator monochromatization
diffraction data is collected with ω-θ scan mode.Carry out the Lp factor and empirical absorption correction to the data obtained, crystalline structure is solved by direct method, and diffraction data reduction and structure elucidation work use SAINT-5.0 and SHELXS-97 program to complete respectively.Crystal data is as follows:
Bond distance's data of crystal
The bond angle data of crystal:
(3), allyl group alkylated reaction application
Get the title complex I (catalytic amount is 20%) of 0.20mmol in the little flask of 25mL, add the dichloromethane solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the allyl trimethyl silane of 0.3mL is added in above-mentioned solution, stirring at normal temperature, after reacting little 120 hours, carry out nmr analysis, transformation efficiency: 32%;
1hNMR (300MHz, CDCl
3) 7.27 ~ 7.33 (m, 5H, Ar-H), 5.79 ~ 5.80 (m, 1H), 5.12 ~ 5.17 (m, 2H ,-CH
2), 4.71 (d, J=5Hz, 1H), 2.49 ~ 2.50 (m, 2H), 2.28 (s, 1H).
(4) Baylis-Hillman reactive applications
Get the title complex I (catalytic amount is 20%) of 0.20mmol in the little flask of 25mL, add the dichloromethane solution of 2 milliliters, then, phenyl aldehyde and the 0.5mL methyl acrylate of 0.1mL is added in above-mentioned solution, stirring at normal temperature, after reacting little 120 hours, carry out nmr analysis, transformation efficiency: 27%;
1hNMR (300MHz, CDCl
3) 7.20 ~ 7.41 (m, 5H, Ar-H), 6.30 (s, 1H), 5.45 (s, 1H), 3.70 (s, 3H), 3.15 (s, 1H).
(5) Henle reaction application
The preparation of 2-nitro-1 phenylethyl alcohol
Get the title complex I (catalytic amount is 20%) of 0.20mmol in the little flask of 25mL, add the absolute methanol solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL is added in above-mentioned solution, stirring at normal temperature, after reacting little 120 hours, carry out nmr analysis, transformation efficiency: 50%;
1hNMR (300MHz, CDCl
3) 7.28 ~ 7.32 (m, 5H, Ar-H), 5.32 ~ 5.35 (d, J=9.18Hz, 1H ,-CH), 4.38 ~ 4.56 (m, 2H ,-CH
2), 3.89 (br, 1H ,-OH).
(6), nitrile silicification reaction application
2-phenyl-2-(three silyloxies) propionitrile
0.2mmol title complex I, II, phenyl aldehyde 0.1mL, TMSCN0.3ml (3.3mmol), 2mL methylene dichloride adds in succession at 20 ~ 30 DEG C, after 5 days, adds shrend and to go out (sherwood oil/methylene dichloride: 5/1) after post layer, obtain colourless oil liquid, productive rate is respectively: 68%;
1hNMR (300MHz, CDCl3) 7.56 – 7.59 (m, 0.9Hz, 2H), 7.31 – 7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H).
13cNMR (75MHz, CDCl3) 136.1,128.8 (x2), 126.2 (x2), 119.1,63.5 ,-0.39 (x3).
Claims (3)
1. one kind by the chirality zinc-nitrogen coordination compound shown in following chemical formula (I):
2. by chirality zinc-nitrogen coordination compound according to claim 1, at 293k temperature, on the X-ray single crystal diffraction instrument of Oxford, with the MoK alpha-ray through graphite monochromator monochromatization
collect diffraction data with ω-θ scan mode, it is characterized in that crystal belongs to rhombic system, spacer P2
12
12
1, unit cell parameters:
α=90 °;
β=90 °;
γ=90 °.
3. chirality zinc-nitrogen coordination compound according to claim 1 shows certain catalytic performance in the allyl group alkylated reaction of phenyl aldehyde, Baylis-Hillman reaction, Henle reaction and silicon cyanation, and its transformation efficiency reaches 32% respectively, and 27%, 50%, 68%.
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| CN201210320992.7A CN102850383B (en) | 2012-04-05 | 2012-09-03 | A kind of chiral zinc nitrogen complexes |
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| CN102977127A (en) * | 2012-12-19 | 2013-03-20 | 罗梅 | Chiral compound |
| CN104327104A (en) * | 2014-10-12 | 2015-02-04 | 罗梅 | Allomorphic chiral zinc complex |
| CN104496929B (en) * | 2014-12-27 | 2016-08-24 | 罗梅 | Chiral zinc complex crystal containing chloroform crystal and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1626524A (en) * | 2003-12-08 | 2005-06-15 | 北京大学 | Dual functions ligand compound of chirality dioxazoline, preparation and application |
| CN102127028A (en) * | 2010-11-24 | 2011-07-20 | 罗梅 | Chiral oxazoline and synthesis method thereof |
| CN102336776A (en) * | 2011-06-07 | 2012-02-01 | 罗梅 | Chiral zinc nitrogen complex |
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| US7847114B2 (en) * | 2004-12-23 | 2010-12-07 | University Of Nebraska At Lincoln | Self-assembled heteroleptic chiral ligands, asymmetric catalyst systems and methods |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1626524A (en) * | 2003-12-08 | 2005-06-15 | 北京大学 | Dual functions ligand compound of chirality dioxazoline, preparation and application |
| CN102127028A (en) * | 2010-11-24 | 2011-07-20 | 罗梅 | Chiral oxazoline and synthesis method thereof |
| CN102336776A (en) * | 2011-06-07 | 2012-02-01 | 罗梅 | Chiral zinc nitrogen complex |
Non-Patent Citations (1)
| Title |
|---|
| Development of Bifunctional Aza-Bis(oxazoline) Copper Catalysts for Enantioselective Henry Reaction;Lang K. et al;《J. Org. Chem.》;20100907;第75卷(第19期);6424–6435 * |
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