CN110078723A - Monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand and its metal complex and preparation method - Google Patents
Monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand and its metal complex and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
Abstract
The present invention relates to a kind of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand and its each preparation methods of metal complex, this method constructs double pyrrole skeleton intermediates through multistep reaction using pyrroles -2- carboxylic acid, ethyl ester as starting material, condensation is carried out with chiral amino alcohol again and is cyclized obtained monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand, and further synthesizes corresponding metal complex using the ligand.Compared with prior art, the present invention is simple and efficient with synthetic method, and synthesis condition is mild, easily operated and reproducible, can largely be prepared.Compared with prior art, ligand of the invention has higher chiral unit utilization rate, while provided synthetic method is simple and efficient, mild condition, it is easily operated and reproducible, the advantages that synthesis difficulty and cost can be substantially reduced, substantially reduce synthesis difficulty and cost.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to a kind of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand
With metal complex and preparation method thereof.
Background technique
In recent decades, the research of asymmetric catalysis synthesis achieves vigorous growth.Chemists' successful development
Thousands of method of asymmetric synthesis, wherein most uses for all relying on chiral ligand.Therefore, chiral ligand is set
Meter and synthesis are the vital links of asymmetry catalysis.Due to currently without pervasive ligand, and many outstanding ligands
With catalyst all by patent protection, industrial application is greatly limited.Therefore it synthesizes with independent intellectual property rights new
Type ligand, studying its complex compound is future on the regularity of catalysis reaction influence and the efficient asymmetry catalysis methodology of development
One of challenging task, has a very important significance.
From 1989, professor's Nishiyama development synthesized a series of using pyridine and the double oxazolines of chirality as skeleton
NNN type pincer ligand py-box passes through the asymmetry catalysis for constantly developing with applying the ligand that can realize that multiclass is reacted
[(a)H.Nishiyama,H.Sakaguchi,T.Nakamura,M.Horihata,M.Kondo,K.Itoh,
Organometallics 1989,8,846-848；(b)G.Desimoni,G.Faita,P.Quadrelli,
Chem.Rev.2003,103,3119-3154.].After this, Guiry group and Du great Ming group independent development benzidine
The double oxazoline tridentate ligand BOPA of the chirality of skeleton.Wherein, professor Guiry mainly studies it in the asymmetry of chromium catalysis
Nozaki-Hiyama-Kishi reaction in application [(a) H.A.McManus, P.J.Guiry, J.Org.Chem.2002,67,
8566-8573；(b)H.A.McManus,P.G.Cozzi,P.J.Guiry,Adv.Synth.Catal.2006,348,551-
558；(c)G.C.Hargaden,H.A.McManus,P.G.Cozzi,P.J.Guiry,Org.Biomol.Chem.2007,5,
763-766；(d)V.Coeffard,M.Aylward,P.J.Guiry,Angew.Chem.Int.Ed.2009,48,9152-
9155.].And big penetrating judgment of shutting out is awarded, its application in asymmetric Henle reaction and Friedel-Crafts alkylation is systematically had studied
[(a)S.-F.Lu,D.-M.Du,S.-W.Zhang,J.Xu,Tetrahedron:Asymmetry 2004,15,3433-3441；
(b)S.-F.Lu,D.-M.Du,S.-W.Zhang,J.Xu,Tetrahedron:Asymmetry 2005,16,1409；(c)S.-
F.Lu,D.-M.Du,J.Xu,Org.Lett.2006,8,2115-2118.].Such NNN type is confirmed by largely reacting example
BOPA ligand has extremely strong chiral control ability in asymmetric catalysis.In recent years, Gade seminar designs and synthesizes
Using isoindoline as the double oxazoline ligand BOXMI of the chirality of skeleton, should with physical efficiency and a variety of transition metal (iron, cobalt, nickel, copper,
Zinc, rhodium) stable complex compound is formed, and corresponding metal complex can not only effectively be catalyzed asymmetric Nozaki-Hiyama-
Kishi reaction can also show unique and outstanding catalysis in a series of acid catalyzed asymmetric electrophilic substitution reaction of Lewis
Effect [(a) Q.-H.Deng, H.Wadepohl, L.H.Gade, Chem.Eur.J.2011,17,14922-14928；(b)Q.-
H.Deng,H.Wadepohl,L.H.Gade,J.Am.Chem.Soc.2012,134,2946-2949；(c)Q.-H.Deng,
H.Wadepohl,L.H.Gade,J.Am.Chem.Soc.2012,134,10769-10772；(d)Q.-H.Deng,T.Bleith,
H.Wadepohl,L.H.Gade,J.Am.Chem.Soc.2013,135,5356-5359；(e)Q.-H.Deng,
C.Rettenmeier,H.Wadepohl,L.H.Gade,Chem.Eur.J.2014,20,93-97]。
In general, the common trait for the NNN type ligand structure reported at present is its double oxazoline chiral unit tool
There is C2Symmetry, this is also exactly the key point of such ligand chiral control.But on the other hand, there is C2The hand of symmetry
Property ligand need two identical chiral unit structures, and in catalytic reaction process only one chiral unit chirality control
It plays a role in system, the utilization rate of chiral unit is only 50%.Meanwhile chiral unit be introduced into be generally ligand synthesis in be most difficult to
Link, and cost of material is high.Therefore, the chiral ligand that design only has single chiral unit accordingly can significantly improve hand
Property unit utilization rate while reduce ligand synthesis difficulty and cost.
Summary of the invention
It can both guarantee hand it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
Property environment can improve the monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand and its metal complex of the chiral unit utilization rate of ligand again
And preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
One of the object of the invention is, provides a kind of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand, which has as logical
Structure shown in Formulas I:
Wherein, R1For C1-10Alkyl or one of aromatic radical；
R2、R3、R4、R5、R6It is respectively and independently selected from as hydrogen, halogen, C1-24Alkyl or one of aromatic radical, and it is any
Adjacent R group can engage that be formed can be with substituted or unsubstituted carbocyclic ring or the ring of heterocycle；
R7、R8It is respectively and independently selected from as hydrogen, C1-10Alkyl or one of aromatic radical, and R7、R8It is different；
Further, the C1-10Alkyl be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, uncle
One of butyl, cyclobutyl, n-pentyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl or suberyl；
The C1-24Alkyl be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, tert-butyl, ring fourth
One of base, n-pentyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl, suberyl or adamantyl；
The aromatic radical includes 1- naphthalene, 2- naphthalene, 1- anthryl, 2- anthryl, 9- anthryl and 9- phenanthryl and phenylOne of,
Wherein Rx、Ry、RzIt is respectively and independently selected from as hydrogen, methyl, methoxyl group, ethyl, ethyoxyl, n-propyl, isopropyl, just
One of butyl, tert-butyl, nitro, trifluoromethyl, cyano, phenyl, mesyl, p-toluenesulfonyl, benzyl or halogen.
The second purpose of the present invention is, a kind of preparation method of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand is provided, including
Following steps:
(1) under the conditions of -10-0 DEG C of anhydrous and oxygen-free, lewis acid and acyl chlorides 8 is dissolved in organic solvent, dripped into system
Pyrroles -2- the carboxylic acid, ethyl ester 2 for being dissolved in organic solvent is added, after being added dropwise completely, system is transferred at 50-90 DEG C and is reacted, TLC is used
Monitoring is to fully reacting, and dry by multiple washing, extraction, column chromatography for separation obtains intermediate 3；
(2) intermediate 3 is dissolved in organic solvent, under the conditions of -10-0 DEG C, reducing agent is added portionwise, after be transferred to
It is reacted at 10-30 DEG C, after TLC monitors fully reacting, is cooled to 0 DEG C, is quenched with saturated sodium bicarbonate aqueous solution, through multiple
Washing, extraction, dry, column chromatography for separation obtains intermediate 4；
(3) intermediate 4 and pyrroles 9 are dissolved in ethyl alcohol containing concentrated hydrochloric acid, are heated to 85-95 DEG C, TLC monitors fully reacting
Afterwards, directly vacuum distillation concentration, column chromatography for separation obtain product Intermediate 5；
(4) intermediate 5 is dissolved under the conditions of going to -10-0 DEG C in organic solvent, it will be slow dissolved with the organic solvent of oxidant
Reaction system is instilled, is added dropwise under the conditions of rear system is then transferred to 10-30 DEG C and is reacted, after TLC monitors fully reacting, is subtracted
Distillation and concentration is pressed, column chromatography for separation obtains intermediate 6；
(5) under the conditions of anhydrous and oxygen-free, by intermediate 6 and chiral amino alcohol 10, at 120-140 DEG C after heating and melting,
Sodium hydride is added, reaction, which is held under pumping state, is reacted, and system directly carries out column chromatography for separation after the reaction was completed, obtains
Intermediate 7；
(6) under the conditions of anhydrous and oxygen-free, intermediate 7 and 4-dimethylaminopyridine are dissolved in organic solvent, dropwise addition is dissolved in
The alkali of organic solvent, system go to 0 DEG C again, and 4- toluene sulfochloride is dissolved in organic solvent, are added drop-wise in reaction system slowly, reaction
System, which is transferred at 10-30 DEG C, reacts, and after TLC monitors fully reacting, directly carries out column chromatography for separation, finally obtains Formulas I ligand.
Further, the pyrroles -2- carboxylic acid, ethyl ester 2, acyl chlorides 8, pyrroles 9, chiral amino alcohol 10 have as general formula 2,
8, structure shown in 9 and 10:
Wherein, R1-R8It defines identical as described in claim 1；
Intermediate 3, intermediate 4, intermediate 5, intermediate 6 and the intermediate 7 has such as 3,4,5,6 and 7 institute of general formula
The structure shown:
Wherein, R1-R8It defines identical as described in claim 1.
The preparation process of ligand of the present invention can be indicated simply with following reaction process by taking general formula I as an example:
Further, pyrroles -2- carboxylic acid, ethyl ester 2 described in step (1), acyl chlorides 8 and lewis acidic molar ratio are 1:
(1-1.5):(1-1.5)；
Intermediate 3 described in step (2) and reducing agent molar ratio are 1:(1.5-6)；
Intermediate 4 described in step (3) and 9 molar ratio of pyrroles are 1:(1-2)；
The ratio of volumes of aqueous ethanol containing concentrated hydrochloric acid described in step (3) is concentrated hydrochloric acid: ethyl alcohol=1:(20-40), wherein dense
Concentration of hydrochloric acid is 12mmol/mL；
Intermediate 5 described in step (4) and oxidant molar ratio are 1:(1.2-1.5)；
Intermediate 6 described in step (5), amino alcohol 10 and sodium hydride molar ratio are 1:(4-5): (2-5)；
Intermediate 7 described in step (6), 4-dimethylaminopyridine, alkali and 4- tosyl cl molar ratio are 1:(0.4-
0.6):(4-6):(3-4)。
Further, the organic solvent include benzene,toluene,xylene, trimethylbenzene, acetonitrile, ether, tetrahydrofuran,
Glycol dimethyl ether, chloroform, methylene chloride, methanol, ethyl alcohol, isopropanol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide
Or one of one or a variety of in dimethyl sulfoxide or 1,2- dichloroethanes；It is preferred that methylene chloride, tetrahydrofuran, acetonitrile, second
One of alcohol, isopropanol, N,N-dimethylformamide or 1,2- dichloroethanes；
The lewis acid includes aluminium chloride, iron chloride, zinc chloride, inidum chloride, boron trifluoride ether solution, phosphoric
One of niobium；It is preferred that one of aluminium chloride, iron chloride or zinc chloride；
The reducing agent includes in sodium borohydride, lithium aluminium hydride, hydrogen, phenyl silane, palladium-carbon catalyst or zinc powder
It is one or more；It is preferred that sodium borohydride or lithium aluminium hydride；
The alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, saleratus,
Sodium hydride, hydrofining, calcium hydride, triethylamine, diethylamine, diisopropyl ethyl amine, tetramethylethylenediamine, N, N- dimethyl benzene
Amine, N, N- diethylaniline, 1,4- diazabicyclooctane, diazabicylo dodecane, 1,4- lupetazin, 1- methyl piperazine
One of pyridine, 1- methylpyrrole, quinoline, pyridine or 4-dimethylaminopyridine are a variety of；It is preferred that 4-dimethylaminopyridine, carbonic acid
One of potassium, sodium hydroxide or triethylamine；
The oxidant include chromium trioxide, sodium dichromate, potassium bichromate, potassium permanganate, manganese dioxide, periodic acid,
Lead tetra-acetate, Swern oxidant, dimethyl sulfoxide, selenium dioxide, Dai Si-Martin's oxidant, the chloro- 5,6- dicyan pair of 2,3- bis-
One of benzoquinones, ammonium persulfate-sodium bisulfate, sodium perchlorate or sodium hypochlorite；It is preferred that manganese dioxide, Dai Si-Martin's oxidant
Or one kind of the chloro- 5,6- dicyanoquinone of 2,3- bis-.
The three of the object of the invention are, provide a kind of using compound shown in Formulas I as the metal complex of ligand, the metal network
Closing object has the structure as shown in general formula II:
Wherein, R1-R8It defines identical as described in claim 1；M is one of transition metal；X matches for anion
Body；N=1,2,3.
Further, the M is one of palladium, copper, rhodium, iridium, iron, nickel or cobalt；The X be halogen, nitrate anion,
Sulfate radical, acetate, p-methyl benzenesulfonic acid root, trifluoromethanesulfonic acid root, hexafluoro-phosphate radical, perchlorate, in acetylacetone,2,4-pentanedione acid group
It is a kind of.
Above-mentioned metal complex is made by the following method: under the conditions of anhydrous and oxygen-free, by the ligand of Formulas I structure and simple gold
Belonging to salt, 1:2 is directly dissolved in anhydrous methanol in molar ratio, is stirred overnight, and anhydrous and oxygen-free filtering, recrystallization obtain Formula II structure
Respective metal complex compound.
Compared with prior art, the present invention is directed to the structural advantages by combining existing NNN pincer ligand, one kind is synthesized
Novel monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand.Only comprising single chiral evil in the Novel Ligands structure of designed invention
Oxazoline ring can not only guarantee chiral environment but also can improve the chiral unit utilization rate of ligand.And in the other side of ligand structure
The steric hindrance and electrical property of entire ligand then are adjusted by introducing steric hindrance and electrically different achirality group, so that it is more
Good stereoselectivity is realized in the catalytic process of class reaction.
It can be seen that the design and development of heretofore described novel monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand will
New approaches can be provided for the design of subsequent chiral ligand and chiral catalyst.Meanwhile synthesize such ligand, study it and metal from
Son coordination and be applied to asymmetric catalysis, have important theory significance and and actual benefit.
Synthetic method of the present invention is simple and efficient, and synthesis condition is mild, easily operated and reproducible, can largely be made
It is standby.Designed ligand is novel monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand, its single chiral unit feature
The utilization efficiency that chiral unit can be improved substantially reduces synthesis difficulty and cost.
Detailed description of the invention
Fig. 1 is the X-Ray of the chiral pincerlike metal complex II-Cu of monosubstituted oxazolyl quinoline ring NNN class
Specific embodiment
The synthesis of chiral monosubstituted oxazolyl quinoline ring NNN type tridentate ligand of the invention is carried out specifically below with reference to specific example
Bright, purpose, which is only that, is best understood from the contents of the present invention, and therefore, the cited case is not intended to limit protection scope of the present invention.
Following DCE represents 1,2- dichloroethanes, DCM represents methylene chloride, PE represents petroleum ether, EA represents ethyl acetate,
Ad represent adamantyl,iPr represents isopropyl, DDQ represents the chloro- 5,6- dicyano -1,4- benzoquinones of 2,3- bis-, DMAP represents 4- bis-
Methylamino pyridine.
Embodiment 1: the synthesis of intermediate 3-1.
Under anhydrous and oxygen-free condition condition of ice bath, zinc chloride (981.4mg, 7.2mmmol) and chlorobenzoyl chloride (1.0121g,
It 7.2mmol) is dissolved in 5mL dichloroethanes, the pyrroles's -2- carboxylic acid, ethyl ester for entering and being dissolved in 1mL dichloroethanes is slowly added dropwise, drips
Quan Hou is transferred in 50 DEG C of oil baths and reacts.TLC monitoring reaction, after fully reacting, is washed with water, methylene chloride extraction, dilute hydrochloric acid water
Solution is washed, and is next washed with saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate is dry, vacuum distillation concentration, column chromatography point
From (PE/EA=10:1), intermediate 3-1 white solid 840mg, yield 72% are obtained.
1H-NMR(600MHz,CDCl3): δ 10.01 (s, 1H), 7.90 (d, J=7.2Hz, 2H), 7.59 (t, J=7.4Hz,
1H), 7.50 (t, J=7.7Hz, 2H), 6.93 (dd, J=3.7,2.8Hz, 1H), 6.84 (dd, J=3.8,2.8Hz, 1H),
4.38 (q, J=7.1Hz, 2H), 1.39 (t, J=7.1Hz, 3H)
Embodiment 2: the synthesis of intermediate 4-1.
Intermediate 3-1 (24.3mg, 0.1mmol) is dissolved in 2mL methanol, under condition of ice bath, sodium borohydride
(15.3mg, 0.4mmol) is added in 30 minutes in three times, is then transferred into room temperature.After TLC monitors fully reacting, it is cooled to 0
DEG C, it is quenched with saturated sodium bicarbonate aqueous solution, ethyl acetate extraction, saturated sodium-chloride water solution is washed, and organic phase is dry, and decompression is steamed
Concentration is evaporated, column chromatography for separation obtains intermediate 4-1 white solid 23.6mg, yield 98%.
1H-NMR(400MHz,CDCl3)δ9.25(s,1H),7.42-7.31(m,5H),6.85-6.81(m,1H),5.98
(t, J=2.9Hz, 1H), 5.89 (d, J=3.1Hz, 1H), 4.29 (q, J=7.1Hz, 2H), 1.34 (t, J=7.1Hz, 3H)
Embodiment 3: the synthesis of intermediate 5-1.
In a round-bottomed flask, intermediate 4-1 (0.3mmol) and 2- adamantyl pyrroles (0.3mmol) are dissolved in 5mL and contain
In the ethanol solution of 0.2mL concentrated hydrochloric acid, 80 DEG C are heated to reflux.After TLC monitors fully reacting, directly vacuum distillation removes solvent,
Column chromatography for separation (PE/EA=30:1) obtains red solid intermediate 5-1.
1H NMR(400MHz,CDCl3) δ 13.38 (s, 1H), 7.48 (d, J=31.0Hz, 5H), 6.87 (d, J=4.0Hz,
1H), 6.79 (d, J=4.6Hz, 1H), 6.64 (d, J=4.6Hz, 1H), 6.23 (d, J=4.0Hz, 1H), 5.30 (s, 1H),
4.38 (q, J=7.1Hz, 2H), 2.04 (s, 7H), 1.85 (d, J=32.3Hz, 8H), 1.41 (t, J=7.1Hz, 3H)
Embodiment 4: the synthesis of intermediate 6-1.
In a round-bottomed flask, intermediate 5-1 (0.15mmol) is dissolved in 15mL methylene chloride, under the conditions of 0 DEG C, 2,3-
Two chloro- 5,6- dicyano-Isosorbide-5-Nitrae-benzoquinones (DDQ, 0.18mmol) are dissolved in 15mL methylene chloride and being slowly added drop-wise in reaction system,
It is transferred to and reacts under room temperature.After TLC monitors fully reacting, directly vacuum distillation concentration, column chromatography for separation (PE/EA=25:
1) red solid intermediate 6-1, yield 75%, are obtained.
1H-NMR(400MHz,CDCl3) δ 13.38 (s, 1H), 7.44 (s, 5H), 6.87 (d, J=3.9Hz, 1H), 6.79
(d, J=4.6Hz, 1H), 6.64 (d, J=4.6Hz, 1H), 6.23 (d, J=3.9Hz, 1H), 4.38 (q, J=7.1Hz, 2H),
2.04 (s, 7H), 1.94-1.70 (m, 8H), 1.41 (t, J=7.1Hz, 3H)
Embodiment 5: the synthesis of intermediate 7-1.
Under the conditions of anhydrous and oxygen-free, in Shrek pipe, intermediate 6-1 (0.09mmol) and D- benzene glycinol is added
(0.36mmol) after 120 DEG C of heating and meltings, is added sodium hydride (200mol%, 0.18mmol), and reaction is anti-under pumping state
It answers, reaction in about 5 minutes is completed, directly progress column chromatography for separation (PE/EA=2:1), obtains product Intermediate 7-1, yield is
75%.
1H-NMR(400MHz,CDCl3) δ 7.57-7.28 (m, 10H), 6.90 (d, J=4.2Hz, 1H), 6.62 (d, J=
2.0Hz, 1H), 6.61 (d, J=2.2Hz, 1H), 6.33 (d, J=4.3Hz, 1H), 5.33 (t, 1H), 4.03 (d, J=5.1Hz,
2H),1.98(s,7H),1.82–1.68(m,8H).
Embodiment 6: intermediate 7-1 obtains ligand i -1.
Under the conditions of anhydrous and oxygen-free, in Shrek pipe, by intermediate 7-1 (0.04mmol) and 4-dimethylaminopyridine
(0.02mmol) is dissolved in 3mL methylene chloride, and triethylamine (0.16mmol) is being added dropwise.Under the conditions of 0 DEG C, 4- toluene sulfochloride
(0.12mmol) is dissolved in 2mL methylene chloride, is slowly added drop-wise in reaction system, and room temperature reaction is transferred to.TLC monitoring has been reacted
Quan Hou is directly concentrated under reduced pressure and carries out column chromatography for separation (PE/EA), obtains final ligand i -1, red solid, yield 82%.
1H-NMR(400MHz,CDCl3)δ13.74(s,1H),7.52–7.40(m,5H),7.39–7.32(m,4H),7.31–
7.27 (m, 1H), 6.82 (dd, J=4.0,0.9Hz, 1H), 6.77 (dd, J=4.6,1.0Hz, 1H), 6.56 (dd, J=4.6,
1.0Hz, 1H), 6.35 (dd, J=4.0,1.0Hz, 1H), 5.46 (t, J=9.0Hz, 1H), 4.83 (t, J=9.1Hz, 1H),
4.28 (t, J=8.3Hz, 1H), 2.07 (s, 3H), 2.04 (s, 6H), 1.78 (s, 6H)；13C NMR(100MHz,CDCl3)δ
179.8,159.3,148.0,142.7,138.1,137.2,137.0,134.8,130.9,129.8,128.9,128.8,
127.9,127.6,126.8,121.8,121.7,114.6,74.7,70.2,41.1,37.0,36.8,28.5；IR(KBr):νmax
2898,2843,1991,1647,1584,1340,1265,1036,978cm-1；
Embodiment 7: ligand i -2, I-3 and I-4.
Ligand i -2, I-3 and I-4 can be prepared respectively according to synthetic method described above, and relevant characterization data are as follows:
Ligand i -1:1H NMR(400MHz,CDCl3)δ7.76–7.66(m,4H),7.54–7.27(m,17H),7.26–
7.15 (m, 6H), 6.81 (d, J=4.1Hz, 1H), 6.45 (d, J=4.5Hz, 1H), 6.23 (d, J=4.1Hz, 1H), 5.85
(d, J=4.5Hz, 1H), 5.45 (dd, J=9.7,8.1Hz, 1H), 4.85 (dd, J=9.6,8.7Hz, 1H), 4.38 (t, J=
8.2Hz,1H)；13C NMR(101MHz,CDCl3)δ166.9,159.0,148.6,143.3,142.5,141.9,141.4,
140.4,138.7,137.1,137.1,133.1,132.6,130.9,130.1,129.6,129.0,129.0,128.9,
128.3,127.9,127.9,127.8,127.7,127.4,127.0,122.1,115.3,74.7,70.5；IR(KBr):νmax
3352,2921,2849,1648,1581,1259,694cm-1；
Ligand i -2:1H NMR(400MHz,CDCl3) δ 12.91 (s, 1H), 7.58 (dd, J=7.4,2.0Hz, 2H),
7.53-7.44 (m, 3H), 7.35-7.32 (m, 2H), 7.29-7.25 (m, 3H), 7.10 (s, 2H), 6.91 (d, J=4.1Hz,
1H), 6.81 (d, J=4.4Hz, 1H), 6.46 (dd, J=7.5,4.2Hz, 2H), 5.35 (dd, J=9.9,8.1Hz, 1H),
4.71 (dd, J=10.0,8.4Hz, 1H), 4.19 (t, J=8.2Hz, 1H), 3.03 (dt, J=13.5,6.7Hz, 2H), 2.95
(dt, J=13.8,6.9Hz, 1H), 1.31 (d, J=6.9Hz, 6H), 1.22 (s, 12H)；13C NMR(101MHz,CDCl3)δ
165.6,159.5,149.4,147.7,146.9,142.5,139.8,138.8,137.3,133.8,133.0,131.1,
130.7,129.1,128.8,127.8,127.7,126.9,126.1,124.2,121.1,116.5,74.8,70.3,34.5,
30.9,24.1；IR(KBr):νmax 2958,2931,2866,1653,1578,1462,1271cm-1；
Ligand i -3:1H NMR(400MHz,CDCl3)δ13.45(s,1H),9.23–9.13(m,1H),8.77–8.71(m,
1H), 8.69 (d, J=8.4Hz, 1H), 8.26 (s, 1H), 7.89 (d, J=7.6Hz, 1H), 7.69 (t, J=7.1Hz, 1H),
7.62-7.54 (m, 5H), 7.55-7.45 (m, 3H), 7.42-7.34 (m, 2H), 7.34-7.28 (m, 3H), 7.16 (d, J=
4.6Hz, 1H), 7.03 (d, J=4.5Hz, 1H), 6.91 (d, J=4.0Hz, 1H), 6.45 (d, J=4.0Hz, 1H), 5.37
(dd, J=9.7,8.4Hz, 1H), 4.71 (dd, J=10.0,8.4Hz, 1H), 4.21 (t, J=8.3Hz, 1H)；13C NMR
(101MHz,CDCl3)δ168.0,158.7,150.3,142.4,139.2,137.1,136.7,135.4,131.3,131.2,
131.1,130.9,130.2,130.0,129.7,129.5,129.2,128.9,128.0,127.9,127.8,127.6,
127.5,127.1,127.0,126.8,126.4,122.9,122.7,122.5,115.0,74.9,70.5；IR(KBr):νmax
2958,2927,2848,1650,1559,1446,1293,1199,979cm-1；
Embodiment 8: the preparation of complex compound II-Cu.
Under the conditions of anhydrous and oxygen-free, by ligand i -1 (0.5mmol) and copper acetate monohydrate in Shrek pipe
(1.0mmol) is directly dissolved in anhydrous methanol, and overnight, anhydrous and oxygen-free filtering, recrystallization obtain red metal complex for reaction
II-Cu, yield 88%.Scheme as shown in Figure 1 for the X-Ray of complex compound II-Cu, as can be seen from the figure double pyrrole skeleton collaborations are single
Chiral oxazoline ring fixed center metallic copper forms rigid planar structure, while on the adamantyl and oxazoline ring of big steric hindrance
Chiral unit each serve as occupy-place and provide chiral environment effect.
Above embodiments are merely to illustrate technical solution of the present invention, are not limitations of the present invention, the art
Change that those of ordinary skill is made within the essential scope of the present invention, substitution, modification, simplification are equivalent transformation, not
It is detached from spirit of the invention, also should belong to claims of the invention.
Claims (10)
1. a kind of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand, which is characterized in that the ligand has the structure as shown in general formula I:
Wherein, R1For C1-10Alkyl or one of aromatic radical；
R2、R3、R4、R5、R6It is respectively and independently selected from as hydrogen, halogen, C1-24Alkyl or one of aromatic radical, and it is any adjacent
R group can engage that be formed can be with substituted or unsubstituted carbocyclic ring or the ring of heterocycle；
R7、R8It is respectively and independently selected from as hydrogen, C1-10Alkyl or one of aromatic radical, and R7、R8It is different.
2. a kind of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand according to claim 1, which is characterized in that the C1-10
Alkyl be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopenta,
One of n-hexyl, cyclohexyl, n-heptyl or suberyl；
The C1-24Alkyl be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, tert-butyl, cyclobutyl, just
One of amyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl, suberyl or adamantyl；
The aromatic radical includes 1- naphthalene, 2- naphthalene, 1- anthryl, 2- anthryl, 9- anthryl and 9- phenanthryl and phenyl
One of,
Wherein Rx、Ry、RzBe respectively and independently selected from for hydrogen, methyl, methoxyl group, ethyl, ethyoxyl, n-propyl, isopropyl, normal-butyl,
One of tert-butyl, nitro, trifluoromethyl, cyano, phenyl, mesyl, p-toluenesulfonyl, benzyl or halogen.
3. a kind of preparation method of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand as described in claim 1, which is characterized in that
The following steps are included:
(1) under the conditions of -10-0 DEG C of anhydrous and oxygen-free, lewis acid and acyl chlorides 8 is dissolved in organic solvent, are added dropwise into system
It is dissolved in the pyrroles -2- carboxylic acid, ethyl ester 2 of organic solvent, after being added dropwise completely, system is transferred at 50-90 DEG C and is reacted, is monitored with TLC
To fully reacting, dry by multiple washing, extraction, column chromatography for separation obtains intermediate 3；
(2) intermediate 3 is dissolved in organic solvent, under the conditions of -10-0 DEG C, reducing agent is added portionwise, after be transferred to 10-30
It is reacted at DEG C, after TLC monitors fully reacting, is cooled to 0 DEG C, is quenched with saturated sodium bicarbonate aqueous solution, repeatedly washed,
Extraction, dry, column chromatography for separation obtains intermediate 4；
(3) intermediate 4 and pyrroles 9 are dissolved in ethyl alcohol containing concentrated hydrochloric acid, are heated to 85-95 DEG C, after TLC monitors fully reacting, directly
Vacuum distillation concentration is connect, column chromatography for separation obtains product Intermediate 5；
(4) intermediate 5 is dissolved under the conditions of going to -10-0 DEG C in organic solvent, will be instilled slowly dissolved with the organic solvent of oxidant
Reaction system is added dropwise under the conditions of rear system is then transferred to 10-30 DEG C and is reacted, and after TLC monitors fully reacting, decompression is steamed
Concentration is evaporated, column chromatography for separation obtains intermediate 6；
(5) under the conditions of anhydrous and oxygen-free, intermediate 6 and chiral amino alcohol 10 at 120-140 DEG C after heating and melting, are added
Sodium hydride, reaction, which is held under pumping state, is reacted, and system directly carries out column chromatography for separation after the reaction was completed, obtains centre
Body 7；
(6) under the conditions of anhydrous and oxygen-free, intermediate 7 and 4-dimethylaminopyridine are dissolved in organic solvent, dropwise addition is dissolved in organic
The alkali of solvent, system go to 0 DEG C again, and 4- toluene sulfochloride is dissolved in organic solvent, is added drop-wise in reaction system slowly, reaction system
It is transferred at 10-30 DEG C and reacts, after TLC monitors fully reacting, directly carry out column chromatography for separation, finally obtain Formulas I ligand.
4. a kind of preparation method of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand according to claim 3, feature exist
In the pyrroles -2- carboxylic acid, ethyl ester 2, acyl chlorides 8, pyrroles 9, chiral amino alcohol 10 have to be tied as shown in general formula 2,8,9 and 10
Structure:
Wherein, R1-R8It defines identical as described in claim 1.
5. a kind of preparation method of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand according to claim 3, feature exist
In the intermediate 3, intermediate 4, intermediate 5, intermediate 6 and intermediate 7 have to be tied as shown in general formula 3,4,5,6 and 7
Structure:
Wherein, R1-R8It defines identical as described in claim 1.
6. a kind of preparation method of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand according to claim 3, feature exist
In pyrroles -2- carboxylic acid, ethyl ester 2 described in step (1), acyl chlorides 8 and lewis acidic molar ratio are 1:(1-1.5): (1-
1.5)；
Intermediate 3 described in step (2) and reducing agent molar ratio are 1:(1.5-6)；
Intermediate 4 described in step (3) and 9 molar ratio of pyrroles are 1:(1-2)；
The ratio of volumes of aqueous ethanol containing concentrated hydrochloric acid described in step (3) is concentrated hydrochloric acid: ethyl alcohol=1:(20-40), wherein concentrated hydrochloric acid
Concentration is 12mmol/mL；
Intermediate 5 described in step (4) and oxidant molar ratio are 1:(1.2-1.5)；
Intermediate 6 described in step (5), amino alcohol 10 and sodium hydride molar ratio are 1:(4-5): (2-5)；
Intermediate 7 described in step (6), 4-dimethylaminopyridine, alkali and 4- tosyl cl molar ratio are 1:(0.4-
0.6):(4-6):(3-4)。
7. a kind of preparation method of monosubstituted oxazolyl quinoline ring NNN class chirality pincer ligand according to claim 3, feature exist
In the organic solvent includes benzene,toluene,xylene, trimethylbenzene, acetonitrile, ether, tetrahydrofuran, glycol dimethyl ether, chlorine
Imitative, methylene chloride, methanol, ethyl alcohol, isopropanol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,
One of 2- dichloroethanes is a variety of；
The lewis acid include aluminium chloride, iron chloride, zinc chloride, inidum chloride, boron trifluoride ether solution, in columbium pentachloride
One kind；
The reducing agent includes one of sodium borohydride, lithium aluminium hydride, hydrogen, phenyl silane, palladium-carbon catalyst or zinc powder
Or it is a variety of；
The alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, saleratus, hydrogenation
Sodium, hydrofining, calcium hydride, triethylamine, diethylamine, diisopropyl ethyl amine, tetramethylethylenediamine, N, accelerine, N,
N- diethylaniline, 1,4- diazabicyclooctane, diazabicylo dodecane, 1,4- lupetazin, 1- methyl piperidine, 1-
One of methylpyrrole, quinoline, pyridine or 4-dimethylaminopyridine are a variety of；
The oxidant includes chromium trioxide, sodium dichromate, potassium bichromate, potassium permanganate, manganese dioxide, periodic acid, four vinegar
Lead plumbate, Swern oxidant, dimethyl sulfoxide, selenium dioxide, Dai Si-Martin's oxidant, the chloro- 5,6- dicyanoquinone of 2,3- bis-,
One of ammonium persulfate-sodium bisulfate, sodium perchlorate, sodium hypochlorite.
8. a kind of chiral pincerlike metal complex of monosubstituted oxazolyl quinoline ring NNN class, which is characterized in that the complex compound uses such as claim
Ligand described in book 1 is formed with metal complex, has the structure as shown in general formula II:
Wherein, R1-R8It defines identical as described in claim 1；M is one of transition metal；X is anion ligand；n
=1,2,3.
9. the chiral pincerlike metal complex of a kind of monosubstituted oxazolyl quinoline ring NNN class according to claim 8, which is characterized in that institute
The M stated is one of palladium, copper, rhodium, iridium, iron, nickel or cobalt.
10. the chiral pincerlike metal complex of a kind of monosubstituted oxazolyl quinoline ring NNN class according to claim 8, which is characterized in that institute
The X stated is halogen, nitrate anion, sulfate radical, acetate, p-methyl benzenesulfonic acid root, trifluoromethanesulfonic acid root, hexafluoro-phosphate radical, perchloric acid
One of root, acetylacetone,2,4-pentanedione acid group.
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