CN102690279A

CN102690279A - Chiral zinc complex

Info

Publication number: CN102690279A
Application number: CN2012101844535A
Authority: CN
Inventors: 罗梅
Original assignee: Individual
Current assignee: Individual
Priority date: 2012-06-06
Filing date: 2012-06-06
Publication date: 2012-09-26
Also published as: CN102887912B; CN102887912A

Abstract

The invention discloses a chiral complex. The complex has the chemical formula shown in the specifications. A method for synthesizing the complex comprises the following steps of: refluxing 6-methyl-2-cyano-3-hydroxypyridine and L-leucinol to react in chlorobenzene solvent under water and oxygen-free conditions and in the presence of a catalyst anhydrous ZnCl2(133 mol percent) for 48 hours, separating, purifying, after reaction, removing chlorobenzene, adding water and dissolving, extracting by using chloroform, desolventizing an extraction phase, and purifying by column chromatography; and leaching a complex (1) by using petroleum ether and dichloromethane, performing column chromatographic separation, and naturally volatilizing to obtain complex single crystals.

Description

A kind of chirality Zn complex

One, technical field

The present invention relates to a kind of metal organic coordination compounds (title complex) and preparation method thereof, particularly nitrogenous chiral metal organic coordination compound and preparation method thereof exactly is a kind of chirality zinc-nitrogen coordination compound and compound 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 the present organic chemistry, is widely used in the organic synthesis.Use chiral ligand and the catalytic asymmetric catalysis synthesis of transition metal complex that the later stage sixties 20 century occurs have quickened the research of chiral drug greatly.The important content of chemical catalysis asymmetric synthesis method is chiral ligand and containing metal catalyst design, thereby makes reaction have efficient and high enantioselectivity.Usually the used part Shi oxazoline of asymmetric catalyst, Jin Lai oxazoline Zn complex is synthetic and obtain catalytic effect preferably by extensively.

Reference:

1.?Ir(I)?complexes?with?oxazoline-thioether?ligands:?nucleophilic?attack?of?pyridine?on?coordinated?1,5-cyclooctadiene?and?application?as?catalysts?in?imine?hydrogenation,?Guiu,?Ester;?Claver,?Carmen;?Castillon,?Sergio,?Journal?of?Organometallic?Chemistry ,?689(11),?1911-1918。

?2.?Chiral?bis(oxazoline)?complexes.?Synthesis,?structure?and?applications?in?catalytic?phospho-transfer,?Jiang,?M.;?Dalgarno,?S.;?Kilner,?C.?A.;?Halcrow,?M.?A.;?Kee,?T.?P.?Polyhedron ,?20(17),?2151-2162。

?3.?New?Bis(oxazolinyl)phenyl-Ruthenium(II)?Complexes?and?Their?Catalytic?Activity?for?Enantioselective Hydrogenation?and?Transfer?Hydrogenation?of?Ketones,?Ito,?Jun-ichi;?Ujiie,?Satoshi;?Nishiyama,?Hisao,? Organometallics ,?28(2),630-638.

4. Lewis?Acid-Catalyzed?Enantioselective?Hydroxylation?Reactions?of?Oxindoles?and?β-Keto?Esters

Using?DBFOX?Ligand，Ishimaru,?Takehisa;?Shibata,?Norio;?Nagai,?Jun;?Nakamura,?Shuichi;?Toru,?Takeshi;

Kanemasa,?Shuji,?Journal?of?the?American?Chemical?Society ，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.

The alleged chirality Zn complex of the present invention be four [6-methyl-3-(4-isobutyl--4,5-dihydro)-2-oxazolinyl-pyridine-2-phenol] Zn complex by 6-methyl-2-cyano-3-hydroxy pyridine preparation by the title complex shown in the following chemical formula:

Figure 2012101844535100002DEST_PATH_IMAGE002

Chemical name: [6-methyl-3-(4-isobutyl--4,5-dihydro)-2-oxazolinyl-pyridine-2-phenol] Zn complex, be called for short title complex (I).

Figure 2012101844535100002DEST_PATH_IMAGE004

The compound method of this title complex (I) comprises reaction, separation and purifying, it is characterized in that by 6-methyl-2-cyano-3-hydroxy pyridine and L-leucinol under the anhydrous and oxygen-free condition with the anhydrous ZnCl of catalyzer ₂Back flow reaction 48 hours is from, purifying in chlorobenzene solvent when (133 mol%), i.e. reaction is sloughed chlorobenzene after finishing, and chloroform extraction is used in the back that is dissolved in water, and uses column chromatography purification behind the extraction phase precipitation;

The compound method of this title complex (I) is a 6-methyl-2-cyano-3-hydroxy pyridine and L-leucinol back flow reaction 48 hours in chlorobenzene solvent.Title complex (I) is with sherwood oil and eluent methylene chloride, column chromatography for separation, volatilize naturally complex monocrystal.

Four, description of drawings

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

Five, embodiment

The preparation of (one) four [6-methyl-3-(4-isobutyl--4,5-dihydro)-2-oxazolinyl-pyridine-2-phenol] Zn complex

In the 100mL two-mouth bottle, under the anhydrous and oxygen-free condition, add anhydrous ZnCl ₂1.50g (9.74mmol), the 40mL chlorobenzene, 6-methyl-2-cyano-3-hydroxy pyridine 1.0g (7.45mmol), L-leucinol 4.0 g, with the mixture 48h that at high temperature refluxes, stopped reaction, decompression is desolvated to remove,, residuum is used water dissolution, and uses CHCl ₃(20mLx2) extraction, organic phase is used anhydrous sodium sulfate drying, and rotation removes and desolvates, and thick product with sherwood oil/methylene dichloride (1:9) column chromatography, is got white crystal, productive rate 45%; [a] ⁵ _D=+30.0o (c=0.08 THF): IR: 2957,2929,2870,1648,1579,1490; 1386,1322,1284,1250,1205,1153; 1077,1060,953,883,787,749; 707,620,595,419 ultimate analyses: C:49.08 %, H:6.12 %, N:7.99 %.

(3), the nitrile silicification reaction is used

2-phenyl-2-(three silyloxies) propionitrile

0.1mmol title complex I, phenyl aldehyde 0.1mL, TMSCN 0.3 ml (3.3mmol); The 2mL methylene dichloride adds under 20 ~ 30 C in succession, after 5 days, adds the shrend (sherwood oil/methylene dichloride: 5/1) behind the post layer that goes out; Get colourless oil liquid, productive rate is respectively: 26.3%; ¹H NMR (300MHz, CDCl ₃) 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

1. chirality Zn complex is characterized in that: by 6-methyl-2-cyano-3-hydroxy pyridine and L-leucinol under the anhydrous and oxygen-free condition with the anhydrous ZnCl of catalyzer ₂When (133 mol%) in chlorobenzene solvent back flow reaction 48 hours, by the title complex shown in the following chemical formula (II):

（I）。

2. by the compound method of the described title complex of claim 1 (I), by 6-methyl-2-cyano-3-hydroxy pyridine and L-leucinol under the anhydrous and oxygen-free condition with the anhydrous ZnCl of catalyzer ₂Back flow reaction 48 hours is from, purifying in chlorobenzene solvent when (133 mol%), i.e. reaction is sloughed chlorobenzene after finishing, and chloroform extraction is used in the back that is dissolved in water, and uses column chromatography purification behind the extraction phase precipitation; Title complex (I) is with sherwood oil and eluent methylene chloride, column chromatography for separation, volatilize naturally complex monocrystal.