CN105130842A - Novel chiral polydentate ligand, metal-organic coordination polymer formed through coordination, and application of metal-organic coordination polymer - Google Patents

Novel chiral polydentate ligand, metal-organic coordination polymer formed through coordination, and application of metal-organic coordination polymer Download PDF

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CN105130842A
CN105130842A CN201510460173.6A CN201510460173A CN105130842A CN 105130842 A CN105130842 A CN 105130842A CN 201510460173 A CN201510460173 A CN 201510460173A CN 105130842 A CN105130842 A CN 105130842A
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chiral
coordination polymer
organic coordination
metal organic
phenyl
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CN105130842B (en
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涂涛
孙喆明
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Fudan University
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Fudan University
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Abstract

The invention belongs to the technical field of heterogeneous catalysts, and specifically relates to design and synthesis of a novel chiral polydentate ligand, a novel chiral metal-organic coordination polymer, which is prepared through the coordination-driven self-assembly between the chiral polydentate ligand and a metal precursor, and an application of the polymer as a heterogeneous catalyst in asymmetric epoxide ring-opening reactions for preparing chiral amino alcohol. The provided chiral coordination polymer prepared from the chiral polydentate ligand can be used to catalyze the asymmetric epoxide ring-opening reactions so as to prepare chiral amino alcohol efficiently and high-selectively. The novel self-supported catalyst system combines the advantages of homogenous catalysis and heterogeneous catalysis, can prepare chiral amino alcohol under mild conditions, can be recycled efficiently and reused for several times, and has a good application prospect in catalytic chiral amino alcohol preparation in industry.

Description

The metal organic coordination polymer catalyzer that novel chiral polydentate ligand, coordination are formed and application thereof
Technical field
The invention belongs to heterogeneous catalyst technical field, be specifically related to the Design and synthesis of a class novel chiral polydentate ligand, the class novel chiral metal organic coordination polymer that this kind of part and metal precursor are prepared by Coordinate self-assembly and the application prepared at asymmetric epoxy addition as heterogeneous catalyst in chiral amino alcohol.
Background technology
Chiral amino alcohol all shows very important effect effect and purposes in fields such as organic synthesis, chemical pharmacy, biology, chemical industry.Many amino alcohols all have good pharmacologically active, are widely used in the aspects such as medicine, agricultural chemicals, biology, chemical industry.Chiral amino alcohol is also a kind of chiral ligand with excellent fit capability simultaneously, is common in each organic micromolecule asymmetry catalysis.Therefore by the high method preparing chiral amino alcohol of simple conversion, there is important theoretical significance and actual application value.Wherein amino-1,3,4-trihydroxybutane (ABT) of chirality 2-has two chiral centres, an amino and three hydroxyls, is a kind of important C4 organic synthesis fragment, may be used for synthesizing multiple important bioactive molecules, as viracept see nelfinaivr etc.
The asymmetry catalysis ring-opening reaction being raw material with racemic epoxide propane cheap and easy to get is one of common methods that a step builds chiral amino alcohol, has the advantage such as efficient, highly selective, atom economy, environmental protection.Larger development has been had in recent years with the research of chirality Louis acid catalysis epoxy addition, especially using titanic as Louis acid catalysis center, with N, N'-ethylenebis (salicylimines) (Salen), 1,1 '-dinaphthol (Binol) etc. achieve good result of study as the catalyst system of chiral ligand.Due to this kind of homogeneous catalysis system have efficiently, the advantage such as highly selective, paid close attention to widely.Because amino alcohol is in application pharmaceutically, do not allow to there is metal residual in product, therefore how to reclaim catalyzer to avoid the pollution of metal pair product and avoid the waste of expensive chiral metal catalyst and reach reusable object, be all the major issue that must solve before these class methods are applied to industrial production all the time.Reported existing in this kind of organometallic catalytic center-point load to organic polymer, zeolite, ferromagnetic or dendrimer.Although these traditional chirality carrying methods can solve the problem of catalyst recovery on partial extent, also exist obviously reduce with homogeneous catalyst phase specific catalytic activity and selectivity, a series of problem such as charge capacity is low, catalyst cupport uniformity is poor, catalyzer easy in inactivation, recovered frequency are lower, load poor repeatability.
Summary of the invention
The present invention, by the method for transition metal-catalyzed coupling, has first prepared the bridge ligand that a class contains two kinds of chiral centres of Salen and Binol.This bridge ligand can efficiently prepare the novel both hands self-supported catalyst of a class with various metals precursor by the mode that coordination is assembled, thus reaches chiral amino alcohol one step by the asymmetry catalysis ring-opening reaction that catalyze propylene oxide is raw material and build and catalyst recovery and reusable object.By the efficient preparation of this kind of novel both hands self-supported catalyst, transition metal-catalyzed active centre not only can be made to be dispersed in metal coordinating polymer, and high catalytic activity and the selectivity of homogeneous catalyst can be kept very well.In addition, this kind of coordination polymer type catalyzer solubleness in common organic solvents and water is extremely low, the efficient sharp separation of product and catalyzer not only can be realized conveniently by the method for filtering, and repeatedly can reclaim and reuse, thus decrease chiral catalyst waste, effectively reduce metal pair product pollution, meet demand of industrial production.This catalyzer can catalysis benzylamine be to the efficient highly selective chirality addition ring-opening reaction of 3,5,8-trioxa-two ring [5,1,0] octane under mild conditions, and the product of gained, can for the synthesis of ABT molecule through simple deprotection steps.
An object of the present invention there is provided a kind of novel chiral polydentate ligand and synthetic method thereof.
Another object of the present invention be to provide first stability good, urge active high, selectivity good, can the related manufacturing processes of high efficiente callback and reusable novel both hands metal-complexing assembling supported catalyst.
Of the present invention also have an object to be to provide a kind of reaction utilizing the chirality open loop of this kind of novel both hands self-supported catalyst catalysis epoxidation compound.
For solving the problems of the technologies described above, embodiments of the present invention provide a class chirality polydentate ligand, and its structure is as follows, are designated as general formula (I):
Wherein:
X, Y are-O-CH independently of one another, without interfering with each other 2-,-N=CH-or-NH-CH 2-;
W is that phenyl or two ends are connected to A respectively, B two carbon and nitrogen atoms-(CH 2) 4-;
Linker is that carbon carbon is single, double, triple bond directly connects, C 1-8alkyl, to phenyl, a phenyl, adjacent phenyl, Isosorbide-5-Nitrae-divinyl phenyl, ethenylphenyl, ethynyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, Isosorbide-5-Nitrae-methylene radical phenyl or 9,10-anthryl;
R to be carbon number be 1 ~ 12 chain alkyl, carbon number be 5 ~ 7 cyclic alkane base, benzyl or aryl;
Its chirality is by (A a, B a, A, B) order, comprise (R a, R a, R, R), (S a, R a, R, R), (R a, S a, R, R), (R a, R a, S, R), (R a, R a, R, S), (S a, S a, R, R), (S a, R a, S, R), (S a, R a, R, S), (R a, S a, S, R), (R a, S a, R, S), (R a, R a, S, S), (R a, S a, S, S), (S a, R a, S, S), (S a, S a, R, S), (S a, S a, S, R), (S a, S a, S, S), structure is shown below:
Embodiments of the present invention provide the synthetic method of above-mentioned polydentate ligand simultaneously; the present invention is after the linked reaction coupling by the 6-halo of palladium chtalyst, BINOL and the 4-alkynyl salicylic aldehyde of methoxymethyl protection; deprotection in acid condition, then be condensed into imines with chiral diamine thus reach the object of synthesizing both hands bridge ligand.For the Salen-Binol bridge ligand that alkynyl connects, its synthesis step simply can be expressed as follows formula:
Starting material compound 1 and analogue thereof are according to document [X.Wang, X.Wang, H.Guo, Z., K.Ding, Chem.Eur.J., 2005,11,4078 – 4088.] and [L.Ma, P.S.White, W.Lin, J.Org.Chem., 2002,67,75777586.] synthesize, starting raw material 2 and analogue thereof are according to document [H.Michael, W.Marcus, J.Org.Chem., 2006,71,1825-1836] synthesis.
In basic organic solution, at PdCl 2(PPh 3) 2under catalysis, there is Sonogashira linked reaction in alkynyl compounds 1 and bromo compound 2, generates compound 3.Compound 3 sloughs methoxymethyl protecting group under strongly acidic conditions, generates compound 4.The reflux dewatering condensation in organic solution of compound 4 and chiral diamine forms bridge ligand 6.
Embodiments of the present invention provide a kind of preparation method of multiple tooth both hands metal organic coordination polymer simultaneously, and its structure is as follows, are designated as general formula (II):
Wherein:
M 1, M 2for transition metal;
X, Y are-O-CH independently of one another, without interfering with each other 2-,-N=CH-or-NH-CH 2-;
Q is assistant ligand;
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion;
W is that phenyl or two ends are connected to A respectively, B two carbon atoms-(CH 2) 4-;
Linker is that carbon carbon is single, double, triple bond directly connects, C 1-8alkyl, to phenyl, a phenyl, adjacent phenyl, Isosorbide-5-Nitrae-divinyl phenyl, ethenylphenyl, ethynyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, Isosorbide-5-Nitrae-methylene radical phenyl or 9,10-anthryl;
R to be carbon number be 1 ~ 12 chain alkyl, carbon number be 5 ~ 7 cyclic alkane base, benzyl or aryl;
N represents the monomer number comprised in metal coordinating polymer; N be more than or equal to 2 natural number.
Its chirality is by (A a, B a, A, B) order, comprise (R a, R a, R, R), (S a, R a, R, R), (R a, S a, R, R), (R a, R a, S, R), (R a, R a, R, S), (S a, S a, R, R), (S a, R a, S, R), (S a, R a, R, S), (R a, S a, S, R), (R a, S a, R, S), (R a, R a, S, S), (R a, S a, S, S), (S a, R a, S, S), (S a, S a, R, S), (S a, S a, S, R), (S a, S a, S, S), structure is shown below:
Preferably, in the structure of the multiple tooth metal coordinating polymer that embodiments of the present invention provide, M 1, M 2represented transition metal can be Eu, Au, Cr, Ir, Mn, Mo, Ni, Os, Rh, Ru, Ti, Pd, Y, Yb, La or Zn, and assistant ligand can be halogen, carbonyl, phenyl ring, luxuriant ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, methyl ethyl diketone negative ion or all kinds of Phosphine ligands.
The above-mentioned chiral metal organic coordination polymer that embodiments of the present invention provide, there is good stability, urge active high, can high efficiente callback and the advantage such as to reuse.
Embodiments of the present invention provide the preparation method of above-mentioned chiral metal organic coordination polymer simultaneously, the steps include: to utilize the Neo Heliopan AP of chirality polydentate ligand to react with metal precursor in the basic conditions, prepare chiral metal organic coordination polymer by coordination assembling;
Its reaction formula is as follows:
Wherein:
In the coordination poly-merization for the preparation of this chiral metal organic coordination polymer that embodiments of the present invention provide, the general formula of metal precursor is MZ aq b, wherein, a is 0,1 or 2; B is 0,1 or 2; The definition of M, Z, Q as hereinbefore.Specifically, used in this reaction metal precursor is preferably: Ag 2o, AgBF 4, AuCl (SMe 2), Cu 2o, CuI, Ni (OAc) 2, Ti (Oi-Pr) 4, NiCl 2, PtCl 2, K 2ptCl 4, CoCl (PPh 3) 3, CoCl 2, FeCl 2, MnCl 2, ZnCl 2, OsH 6(t-Bu 3p) 2, [Ir (COD) Cl] 2, [Ir (COD) OMe] 2, IrCl 33H 2o, [IrCp*Cl 2] 2, Ir (CO) 2(acac), Pd (OAc) 2, PdCl 2(CH 3cN) 2, RuCl 3, [Ru (COD) Cl] 2, [Ru (p-cymene) Cl 2] 2, [Ru (benzene) Cl 2] 2, [Rh (COD) Cl] 2deng.In addition, the molar ratio of part and transition metal is 1:1 ~ 1:4, organic solvent needed for reaction can select methylene dichloride, chloroform, toluene, benzene, tetrahydrofuran (THF), methyl tertiary butyl ether, acetonitrile, N, dinethylformamide, N,N-dimethylacetamide, methyl-2-pyrrolidone or dimethyl sulfoxide (DMSO) equal solvent; In some cases, the mixed solution of two to three kinds of organic solvent above-mentioned can provide better polymerization result.Above-mentioned coordination poly-merization is temperature required is generally-50 ~ 150 DEG C, and the reaction times is recommended as 1 ~ 24 hour.
Specifically, the laboratory operating procedures of this preparation feedback is as follows: at room temperature, polydentate ligand shown in general formula (I) is dissolved in methylene dichloride or other optional solvents, dropwise add the methylene dichloride of respective metal precursor 1 or the solution of other organic solvents, when solution colour changes, reaction system continues to stir, when TLC monitoring is less than part, if M 1and M 2for same metal, then react stopping; As M 1and M 2for different metals, then continue dropwise to add the corresponding methylene dichloride of metal precursor 2 or the solution of other organic solvents.After sinking to the bottom generation, reaction system continues to stir the regular hour, and reaction stops.After cooling, filter, wash, after vacuum-drying, obtain the chiral metal organic coordination polymer shown in general formula (II).
Verify through experiment, logical chiral metal organic coordination polymer shown in formula I, under linker, M, Q, W, X, Y, Z, R, the n in its structure is aforesaid various definition herein or substituent situation, all prepare by above-mentioned coordination poly-merization.
The application of the catalyzer that embodiments of the present invention also provide above-mentioned chiral metal organic coordination polymer to react as asymmetric epoxy addition.Further, the method for this catalytic applications is: under nitrogen atmosphere, and in the reaction system of reaction substrate, organic solvent and water composition, add described chiral metal organic coordination polymer as catalyzer, stirring heating is reacted, obtained chiral amino alcohol; Wherein, reaction substrate is epoxy compounds and primary amine.In above-mentioned reaction, the consumption proportion situation of reaction substrate, water and catalyzer is: the proportioning of epoxy and amine can be 1 ~ 40mmol/mmol, the consumption proportion of organic solvent can be 0 ~ 15mL/mmol substrate, the consumption proportion of water can be 0 ~ 15mL/mmol substrate, and the consumption of catalyzer can be 1 × 10 -3~ 1mmol/mmol substrate, is temperature requiredly generally 0 ~ 80 DEG C, and the reaction times is recommended as 1 ~ 96 hour.
Specifically, the specific operation process that lactic acid is prepared in chiral metal organic coordination polymer catalytic oxidative dehydrogenation reaction embodiments of the present invention provided is as follows:
Under nitrogen atmosphere, chiral metal organic coordination polymer that embodiments of the present invention provide is added successively as supported catalyst, reaction substrate, organic solvent and a certain amount of water in reaction vessel, the post-heating that stirs reacts, after reaction terminates, system is down to room temperature, after centrifugal with low-speed centrifugal device, pour out supernatant liquor, the nearly column chromatography purification of products therefrom is separated.The supported catalyst reclaimed, after organic solvent washing, for subsequent use after vacuum-drying.
Second time circulation time, in the reaction tubes containing dry recovery supported catalyst, rejoins reaction substrate, organic solvent and a certain amount of water, carries out reacting and aftertreatment according to the condition that previous reaction is identical.Circulating reaction like this about 20 times, can't there are how many changes in the selectivity of reaction and transformation efficiency.As can be seen here, catalyzer provided by the present invention can realize reclaiming and recycling well.
To sum up, the present invention utilizes two Binol of the Salen bridging of rigidity as a kind of bridging bidentate ligand, efficiently prepare a kind of novel both hands self-supported catalyst with metal precursor by the mode that coordination is assembled under suitable conditions, thus achieve epoxy compounds asymmetric amine melt ring prepare chiral amino alcohol reaction.This kind of novel both hands self-supported catalyst synthesis is easy, owing to having homodisperse catalytic active center, shows very high catalytic activity and asymmetric selectivity in asymmetric epoxy addition.In addition, the solubleness of this kind of coordination polymer type catalyzer in common solvents is extremely low, not only can carry out being separated of product and catalyzer easily, and repeatedly can reclaim and reuse, meet demand of industrial production, effectively reduce the pollution of heavy metal to environment.
The both hands metal organic coordination polymer of design and synthesis of the present invention is a class novel chiral metal organic coordination assembling supported catalyst, can be used for the reaction of asymmetric epoxy addition, efficiently prepares chiral amino alcohol and derivative thereof.Due to this kind of novel high from load catalyst system stability, be insoluble to most organic solvent and water, multiclass heterogeneous catalytic reaction can be applied to, thus the advantage of homogeneous catalysis and heterogeneous catalysis is combined, not only can realize the synthesis of chiral amino alcohol under mild conditions, and the advantage that there is high efficiente callback and repeatedly recycle.
Accompanying drawing explanation
Fig. 1 is compound 3a prepared in embodiment 1 1hNMR spectrogram.
Fig. 2 is compound 3a prepared in embodiment 1 13cNMR spectrogram.
Fig. 3 is compound 3b prepared in embodiment 2 1hNMR spectrogram.
Fig. 4 is compound 3b prepared in embodiment 2 13cNMR spectrogram.
Fig. 5 is compound 4a prepared in embodiment 3 1hNMR spectrogram.
Fig. 6 is compound 4a prepared in embodiment 3 13cNMR spectrogram.
Fig. 7 is compound 4b prepared in embodiment 4 1hNMR spectrogram.
Fig. 8 is compound 4b prepared in embodiment 4 13cNMR spectrogram.
Fig. 9 is compound 6a prepared in embodiment 5 1hNMR spectrogram.
Figure 10 is compound 6a prepared in embodiment 5 13cNMR spectrogram.
Figure 11 is compound 6b prepared in embodiment 6 1hNMR spectrogram.
Figure 12 is compound 6b prepared in embodiment 6 13cNMR spectrogram.
Figure 13 is the IR spectrogram of compound 7a prepared in embodiment 7.
Figure 14 is the IR spectrogram of compound 7b prepared in embodiment 8.
Figure 15 is the IR spectrogram of compound 7c prepared in embodiment 9.
Figure 16 is the IR spectrogram of compound 7d prepared in embodiment 10.
Figure 17 is the IR spectrogram of compound 7e prepared in embodiment 11.
Figure 18 is the IR spectrogram of compound 7f prepared in embodiment 12.
Figure 19 is the product 8 that in embodiment 15-18, chirality is obtained by reacting from supported catalyst epoxy addition 1hNMR spectrogram.
Figure 20 is the compound 9 that in embodiment 19, derivative reaction obtains 1hNMR spectrogram.
Figure 21 is the HPLC spectrogram of the raceme of product 9 in embodiment 19.
Figure 22 is the HPLC spectrogram of the derivatize product 9 in embodiment 18.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the embodiments of the present invention are explained in detail.But, persons of ordinary skill in the art may appreciate that in each embodiment of the present invention, proposing many ins and outs to make reader understand the application better.But, even without these ins and outs with based on the many variations of following embodiment and amendment, each claim of the application technical scheme required for protection also can be realized.
The preparation of embodiment 1 compound 3a
N 2under protection, add compound 1a (2.2g) with in the 100mLSchlenk bottle of stirrer, compound 2 (4.5g), PdCl successively to drying 2(PPh 3) 2(350mg), PPh 3(130mg), triethylamine 10mL and tetrahydrofuran (THF) 30mL, stirring at room temperature 1 hour.In this solution, add CuI (180mg) again, be heated to 80 DEG C and stir 24h, TLC detection compound 1a disappearance, reaction stops.Product yellow oil 3,2.5g is obtained, productive rate 45% after column chromatography purification. 1HNMR(400MHz,CDCl 3,298K)δ＝11.92(s,1H),9.87(s,1H),8.09(d,J＝1.4,1H),7.95(dd,J＝15.2,9.0,2H),7.89(d,J＝8.1,1H),7.68(d,J＝1.9,1H),7.63(s,1H),7.63(d,J＝1.3,1H),7.60(s,1H),7.58(s,0H),7.39–7.34(m,1H),7.31(dd,J＝8.8,1.6,1H),7.24(dd,J＝6.8,1.3,1H),7.14(dd,J＝8.3,6.2,2H),5.14–5.07(m,2H),5.00(dd,J＝6.8,4.4,2H),3.16(d,J＝1.6,6H),1.44(s,9H). 13CNMR(100MHz,CDCl 3,298K)δ＝196.79,161.20,153.50,152.69,138.91,137.12,135.16,133.95,133.57,131.48,129.90,129.65,128.93,128.76,128.01,126.48,125.82,125.42,124.19,121.38,120.72,120.57,118.53,118.08,117.78,117.60,117.14,114.53,95.15,95.01,88.94,88.38,55.92,29.17.HRMS(ESI/TOF)m/zCalcd.forC 36H 34O 6[M-H] +573.2277；Found:573.2260.[α] D 20＝-25(c1.0,CHCl 3)
The preparation of embodiment 2 compound 3b
N 2under protection, add compound 1b (2.8g) with in the 100mLSchlenk bottle of stirrer, compound 2 (4.5g), PdCl successively to drying 2(PPh 3) 2(350mg), PPh 3(130mg), triethylamine 10mL and tetrahydrofuran (THF) 30mL, stirring at room temperature 1 hour.In this solution, add CuI (180mg) again, be heated to 80 DEG C and stir 24h, TLC detection compound 1b disappearance, reaction stops.Product yellow oil 3b, 5.2g is obtained, productive rate 88% after column chromatography purification. 1HNMR(400MHz,CDCl 3)δ＝11.86(s,1H),9.99(s,1H),8.15(d,J＝1.1,1H),7.99(dd,J＝11.3,9.1,2H),7.92(d,J＝8.1,1H),7.81(d,J＝2.2,1H),7.68–7.62(m,5H),7.60(d,J＝7.8,2H),7.42–7.35(m,2H),7.27(dd,J＝6.8,1.2,1H),7.18(dd,J＝8.6,4.1,2H),5.19–5.10(m,2H),5.03(dd,J＝6.8,4.0,2H),3.19(s,3H),3.19(s,3H),1.51(s,9H). 13CNMR(101MHz,CDCl 3)δ＝197.25,160.90,153.53,152.70,139.72,138.98,133.96,133.62,132.89,132.21,131.61,130.04,129.91,129.64,129.39,129.01,128.85,128.71,128.00,127.31,126.55,125.80,125.42,124.18,122.29,121.39,120.83,118.65,118.10,117.78,117.15,95.17,95.03,90.89,89.25,55.96,55.91,35.11,29.29.[α] D 20＝-21(c1.0,CHCl 3)
The preparation of embodiment 3 compound 4a:
In 50mL round-bottomed flask, add compound 3a (574mg), chloroform 15mL and methyl alcohol 3mL, form yellow solution.Add the hydrochloric acid (3.5mL) of 6M, stirring at room temperature 6 hours, TLC detects starting compound 3a and disappears.Stopped reaction, is neutralized to neutrality with 10% sodium carbonate solution, separatory.Aqueous phase dichloromethane extraction three times, merges organic phase, after anhydrous sodium sulfate drying, after column chromatography purification product yellow solid 4a, 480mg, productive rate 98%. 1HNMR(400MHz,CDCl 3,298K)δ＝11.90(s,1H),9.84(s,1H),8.09(d,J＝1.3,1H),8.00(d,J＝8.9,1H),7.95(d,J＝8.9,1H),7.91(d,J＝7.8,1H),7.69(d,J＝2.0,1H),7.63(d,J＝2.0,1H),7.44–7.36(m,4H),7.36–7.30(m,1H),7.14(t,J＝7.9,2H),1.44(s,9H). 13CNMR(100MHz,CDCl 3,298K)δ＝196.66,161.18,153.71,152.94,138.90,137.18,135.23,133.53,133.19,131.79,131.42,131.04,129.80,129.39,128.99,128.45,127.51,124.60,124.23,124.06,120.43,118.80,118.47,118.05,114.44,111.83,110.88,88.64,88.57,35.03,29.17.HRMS(ESI/TOF)M/zCalcd.forC 36H 34O 6[M-H]573.2277；Found:573.2260.[α] D 20＝+22(c1.0,CHCl 3)
The preparation of embodiment 4 compound 4b:
In 50mL round-bottomed flask, add compound 3b (650mg), chloroform 15mL and methyl alcohol 3mL, form yellow solution.Add the hydrochloric acid (3.5mL) of 6M, stirring at room temperature 6 hours, TLC detects starting compound 3b and disappears.Stopped reaction, is neutralized to neutrality with 10% sodium carbonate solution, separatory.Aqueous phase dichloromethane extraction three times, merges organic phase, after anhydrous sodium sulfate drying, after column chromatography purification product yellow solid 4b, 550mg, productive rate 98%. 1HNMR(400MHz,CDCl 3,298K)δ＝11.82(s,1H),9.93(s,1H),8.14(d,J＝1.5,1H),8.02(d,J＝8.9,1H),7.98(d,J＝8.9,1H),7.94(d,J＝7.6,1H),7.81(d,J＝2.1,1H),7.67–7.62(m,3H),7.60–7.56(m,2H),7.48–7.39(m,4H),7.36(ddd,J＝8.2,6.9,1.4,1H),7.17(dd,J＝8.5,4.8,2H),1.51(s,9H). 13CNMR(101MHz,DMSO-D 6,298K)δ＝199.35,160.19,154.79,153.52,139.45,138.40,134.48,134.29,134.14,132.45,132.39,132.03,130.99,130.84,129.34,128.61,128.40,128.21,126.95,126.46,125.41,124.72,122.83,121.82,121.51,120.24,119.91,119.04,116.27,115.73,115.32,91.52,89.07,35.15,29.52.HRMS(ESI/TOF)M/zCalcd.forC 39H 31O 4[M+H] +563.2222；Found:563.2211.[α] D 20＝+183(c1.0,CHCl 3)
The preparation of embodiment 5 compound 6a:
To in the round-bottomed flask of 50mL drying, add compound 4a (486mg), compound 5 (106mg) and methyl alcohol 10mL.Be heated to return stirring 2 hours, TLC detects raw material and disappears, and stopped reaction, is cooled to room temperature, obtains product yellow solid 6,570mg, 97% after column chromatography purification. 1HNMR(400MHz,CDCl 3,298K)δ＝8.29(s,2H),8.05(d,J＝1.0,2H),7.99(d,J＝8.9,2H),7.91(t,J＝9.5,4H),7.45(d,J＝1.5,2H),7.40(d,J＝1.4,2H),7.39–7.29(m,8H),7.26–7.18(m,12H),7.14(d,J＝8.3,2H),7.09(d,J＝8.7,2H),4.73(s,2H),1.45(s,18H). 13CNMR(101MHz,CDCl 3,298K)δ＝166.46,160.79,153.35,152.79,138.96,137.95,133.49,133.43,133.18,132.81,131.52,131.14,130.04,129.45,129.14,128.52,128.47,128.00,127.83,127.58,124.39,124.20,124.13,119.21,118.51,118.45,117.88,112.67,111.41,110.68,89.79,87.61,80.01,35.01,29.28.[α] D 20＝+216(c1.0,CHCl 3).HRMS(ESI/TOF)M/zCalcd.forC 80H 65N 2O 6[M+H] +1149.4843；Found:1149.4832
The preparation of embodiment 6 compound 6c:
To in the round-bottomed flask of 50mL drying, add compound 4b (486mg), compound 5 (106mg) and methyl alcohol 10mL.Be heated to return stirring 2 disappear, TLC detects raw material and disappears, and stopped reaction, is cooled to room temperature, obtains product yellow solid 6c, 570mg, 97% after column chromatography purification.
The preparation of embodiment 7 both hands self-supported catalyst 7a:
Under nitrogen atmosphere protection, in 25mLSchlenk bottle, add part 6a (114mg) and anhydrous methylene chloride 5mL stirring at room temperature 5 minutes successively.In this yellow solution, dropwise add the dichloromethane solution (0.4mL) of 0.5MTi (Oi-Pr) 4, have orange Precipitation.Dropwise rear continuation stirring at room temperature 12 hours, add deionized water (0.14mL), continue stirring 12 hours, filter, precipitation washed with dichloromethane.Gained solid, through vacuum-drying, obtains orange solid 127mg, productive rate 99%.IR(KBrpellet)ν3432.97,3059.79,2955.16,2348.88,1617.75,1540.5,1497.37,1457.25,1435.37,1405.83,1384.7,1359.64,1341.17,1277.2,1242.27,973.1,819.72,750.26,726.03,697.6,575.21,515.22cm -1.elementalanalysiscalcd(％)for(C 80H 58N 2O 6Ti 2·1.5CH 2Cl 2)n:C,71.64；H,4.50；N,2.05；found:C71.92,H4.74,N,2.04.
The preparation of embodiment 8 both hands self-supported catalyst 7b:
Under nitrogen atmosphere protection, in 25mLSchlenk bottle, add part 6b (114mg) and anhydrous methylene chloride 5mL stirring at room temperature 5 minutes successively.In this yellow solution, dropwise add the dichloromethane solution (0.4mL) of 0.5MTi (Oi-Pr) 4, have orange Precipitation.Dropwise rear continuation stirring at room temperature 12 hours, add deionized water (0.14mL), continue stirring 12 hours, filter, precipitation washed with dichloromethane.Gained solid, through vacuum-drying, obtains orange solid 127mg, productive rate 99%.IR(KBrpellet)ν3422.91,2953.9,2349.567,1618.8,1586.17,1459.23,1440.58,1384.1,1340.43,1242.35,1157.08,1075.85,1002.8,974.63,821.29,749.91,698.72,576.44cm -1；elementalanalysiscalcd(％)for(C 80H 60N 2O 6Ti 2·1.5CH 2Cl 2)n:C,71.53,H,4.64,N,2.05；
The preparation of embodiment 9 both hands self-supported catalyst 7c:
Under nitrogen atmosphere protection, in 25mLSchlenk bottle, add part 6c (130mg) and anhydrous methylene chloride 5mL stirring at room temperature 5 minutes successively.In this yellow solution, dropwise add the dichloromethane solution (0.4mL) of 0.5MTi (Oi-Pr) 4, have orange Precipitation.Dropwise rear continuation stirring at room temperature 12 hours, add deionized water (0.14mL), continue stirring 12 hours, filter, precipitation washed with dichloromethane.Gained solid, through vacuum-drying, obtains orange solid 142mg, productive rate 99%.IR(KBrpellet)ν3444.63,2954.09,2348.97,1614.33,1462.46,1384.47,1342.26,1243.74,668.24,526.18cm -1；elementalanalysiscalcd(％)for(C 92H 66N 2O 6Ti 2·1.5CH 2Cl 2)n:C,73.95；H,4.58；N,1.84；found:C73.71,H4.73,N,1.80.
The preparation of embodiment 10 both hands self-supported catalyst 7d:
Under nitrogen atmosphere protection, in 25mLSchlenk bottle, add part 6d (130mg) and anhydrous methylene chloride 5mL stirring at room temperature 5 minutes successively.In this yellow solution, dropwise add the dichloromethane solution (0.4mL) of 0.5MTi (Oi-Pr) 4, have orange Precipitation.Dropwise rear continuation stirring at room temperature 12 hours, add deionized water (0.14mL), continue stirring 12 hours, filter, precipitation washed with dichloromethane.Gained solid, through vacuum-drying, obtains orange solid 142mg, productive rate 99%.IR(KBrpellet)ν3448.92,2348.83,1618.66,1459.75,1242.00,818.24,579.63,cm -1；elementalanalysiscalcd(％)for(C 92H 68N 2O 6Ti 2·1.5CH 2Cl 2)n:C,73.85；H,4.71；N,1.84；found:C73.67,H4.97,N,1.69.
The preparation of embodiment 11 both hands self-supported catalyst 7e:
Under nitrogen atmosphere protection, in 25mLSchlenk bottle, add part 6e (130mg) and anhydrous methylene chloride 5mL stirring at room temperature 5 minutes successively.In this yellow solution, dropwise add the dichloromethane solution (0.4mL) of 0.5MTi (Oi-Pr) 4, have orange Precipitation.Dropwise rear continuation stirring at room temperature 12 hours, add deionized water (0.14mL), continue stirring 12 hours, filter, precipitation washed with dichloromethane.Gained solid, through vacuum-drying, obtains orange solid 142mg, productive rate 99%.IR(KBrpellet)ν3448.92,2348.83,1618.66,1459.75,1242.00,818.24,579.63,cm -1；elementalanalysiscalcd(％)for(C 92H 68N 2O 6Ti 2·1.5CH 2Cl 2)n:C,73.85；H,4.71；N,1.84；found:C73.67,H4.97,N,1.69.
The preparation of embodiment 12 both hands self-supported catalyst 7f:
Part 6e (130mg) and dehydrated alcohol 5mL stirring at room temperature 5 minutes is added successively in 25mLSchlenk bottle.Mn (OAc) is once added in this yellow solution 24H 2the rapid blackening of O (50mg) solution colour.Return stirring, after 1 hour, is cooled to room temperature, once adds LiCl (21mg), continues return stirring 1 hour under air.Be cooled to room temperature, in this dark solution, dropwise add the dichloromethane solution (0.4mL) of 0.5MTi (Oi-Pr) 4, have Precipitation.Dropwising rear continuation in stirring at room temperature, after 12 hours, adds deionized water (0.14mL), continues stirring 12 hours, filters, precipitation washed with dichloromethane.Gained solid, through vacuum-drying, obtains brown solid 145mg, productive rate 99%.IR(KBrpellet)ν3448.02,2925.51,2360.40,2342.17,1617.86,1529.25,1456.84,1424.02,1403.98,1384.79,1299.52,1172.37,1075.24,735.12,696.93,668.77,576.79,421.98.elementalanalysiscalcd(％)for(C 92H 68ClMnN 2O 7Ti·3CH 2Cl 2)n:C,66.86；H,4.37；N,1.64；found:C66.78,H4.77,N,1.78.
Embodiment 13 novel couples of chiral metal organic coordination assembling supported catalyst 7a are used for the asymmetric epoxy addition amination of catalysis and recycle
Under nitrogen atmosphere protection, in 25mL centrifuge tube, add catalyzer 7a successively, dry toluene 0.5mL, compound 8 (144mg), benzylamine (118mg) and deionized water 7 μ L.At 40 DEG C of heated and stirred reaction 18h, be cooled to room temperature, after adding 6mL ether, centrifugation goes out supernatant liquid, precipitates three times with washed with diethylether, and catalyzer precipitation is for subsequent use after vacuum-drying.Merge organic phase, column chromatography for separation goes out product colorless oil 250mg, productive rate 99%.Be ee=89% by measuring its optical purity with HPLC after the mode derivatize of embodiment 19.Again add dry toluene 0.5mL, compound 8 (144mg) to the catalyzer 7a reclaimed, benzylamine (118mg) and deionized water 7 μ L, react next time. 1HNMR(400MHz,CDCl 3,298K)δ＝7.42–7.28(m,5H),3.98(d,J＝13.2,1H),3.88–3.80(m,3H),3.65–3.52(m,3H),2.61(td,J＝5.4,1.6,1H),1.39(s,3H),1.38(s,3H).MS(EI)m/zcalculated:251.1,found:251.0.
Embodiment 14 novel couples of chiral metal organic coordination assembling supported catalyst 7b are used for the asymmetric epoxy addition amination of catalysis and recycle
Under nitrogen atmosphere protection, in 25mL centrifuge tube, add catalyzer 7b successively, dry toluene 0.5mL, compound 8 (144mg), benzylamine (118mg) and deionized water 7 μ L.At 40 DEG C of heated and stirred reaction 18h, be cooled to room temperature, after adding 6mL ether, centrifugation goes out supernatant liquid, precipitates three times with washed with diethylether, and catalyzer precipitation is for subsequent use after vacuum-drying.Merge organic phase, column chromatography for separation goes out product colorless oil 250mg, productive rate 99%.Be ee=91% by measuring its optical purity with HPLC after the mode derivatize of embodiment 19.Again add dry toluene 0.5mL, compound 8 (144mg) to the catalyzer 7b reclaimed, benzylamine (118mg) and deionized water 7 μ L, react next time. 1HNMR(400MHz,CDCl 3,298K)δ＝7.42–7.28(m,5H),3.98(d,J＝13.2,1H),3.88–3.80(m,3H),3.65–3.52(m,3H),2.61(td,J＝5.4,1.6,1H),1.39(s,3H),1.38(s,3H).MS(EI)m/zcalculated:251.1,found:251.0.
Embodiment 15 novel couples of chiral metal organic coordination assembling supported catalyst 7c are used for the asymmetric epoxy addition amination of catalysis and recycle
Under nitrogen atmosphere protection, in 25mL centrifuge tube, add catalyzer 7c successively, dry toluene 0.5mL, compound 8 (144mg), benzylamine (118mg) and deionized water 7 μ L.At 40 DEG C of heated and stirred reaction 18h, be cooled to room temperature, after adding 6mL ether, centrifugation goes out supernatant liquid, precipitates three times with washed with diethylether, and catalyzer precipitation is for subsequent use after vacuum-drying.Merge organic phase, column chromatography for separation goes out product colorless oil 250mg, productive rate 99%.Be ee=93% by measuring its optical purity with HPLC after the mode derivatize of embodiment 19.Again add dry toluene 0.5mL, compound 8 (144mg) to the catalyzer 7c reclaimed, benzylamine (118mg) and deionized water 7 μ L, react next time. 1HNMR(400MHz,CDCl 3,298K)δ＝7.42–7.28(m,5H),3.98(d,J＝13.2,1H),3.88–3.80(m,3H),3.65–3.52(m,3H),2.61(td,J＝5.4,1.6,1H),1.39(s,3H),1.38(s,3H).MS(EI)m/zcalculated:251.1,found:251.0.
Embodiment 16 novel couples of chiral metal organic coordination assembling supported catalyst 7d are used for the asymmetric epoxy addition amination of catalysis and recycle
Under nitrogen atmosphere protection, in 25mL centrifuge tube, add catalyzer 7d successively, dry toluene 0.5mL, compound 8 (144mg), benzylamine (118mg) and deionized water 7 μ L.At 40 DEG C of heated and stirred reaction 18h, be cooled to room temperature, after adding 6mL ether, centrifugation goes out supernatant liquid, precipitates three times with washed with diethylether, and catalyzer precipitation is for subsequent use after vacuum-drying.Merge organic phase, column chromatography for separation goes out product colorless oil 250mg, productive rate 99%.Be ee=93% by measuring its optical purity with HPLC after the mode derivatize of embodiment 19.Again add dry toluene 0.5mL, compound 8 (144mg) to the catalyzer 7d reclaimed, benzylamine (118mg) and deionized water 7 μ L, react next time. 1HNMR(400MHz,CDCl 3,298K)δ＝7.42–7.28(m,5H),3.98(d,J＝13.2,1H),3.88–3.80(m,3H),3.65–3.52(m,3H),2.61(td,J＝5.4,1.6,1H),1.39(s,3H),1.38(s,3H).MS(EI)m/zcalculated:251.1,found:251.0.
Embodiment 17 novel couples of chiral metal organic coordination assembling supported catalyst 7e are used for the asymmetric epoxy addition amination of catalysis and recycle
Under nitrogen atmosphere protection, in 25mL centrifuge tube, add catalyzer 7e successively, dry toluene 0.5mL, compound 8 (144mg), benzylamine (118mg) and deionized water 7 μ L.At 40 DEG C of heated and stirred reaction 18h, be cooled to room temperature, after adding 6mL ether, centrifugation goes out supernatant liquid, precipitates three times with washed with diethylether, and catalyzer precipitation is for subsequent use after vacuum-drying.Merge organic phase, column chromatography for separation goes out product colorless oil 250mg, productive rate 99%.Be ee=67% by measuring its optical purity with HPLC after the mode derivatize of embodiment 19.Again add dry toluene 0.5mL, compound 8 (144mg) to the catalyzer 7e reclaimed, benzylamine (118mg) and deionized water 7 μ L, react next time. 1HNMR(400MHz,CDCl 3,298K)δ＝7.42–7.28(m,5H),3.98(d,J＝13.2,1H),3.88–3.80(m,3H),3.65–3.52(m,3H),2.61(td,J＝5.4,1.6,1H),1.39(s,3H),1.38(s,3H).MS(EI)m/zcalculated:251.1,found:251.0.
Embodiment 18 novel couples of chiral metal organic coordination assembling supported catalyst 7f are used for the asymmetric epoxy addition amination of catalysis and recycle
Under nitrogen atmosphere protection, in 25mL centrifuge tube, add catalyzer 7f successively, dry toluene 0.5mL, compound 8 (144mg), benzylamine (118mg) and deionized water 7 μ L.At 40 DEG C of heated and stirred reaction 18h, be cooled to room temperature, after adding 6mL ether, centrifugation goes out supernatant liquid, precipitates three times with washed with diethylether, and catalyzer precipitation is for subsequent use after vacuum-drying.Merge organic phase, column chromatography for separation goes out product colorless oil 250mg, productive rate 55%.Be ee=85% by measuring its optical purity with HPLC after the mode derivatize of embodiment 19.Again add dry toluene 0.5mL, compound 8 (144mg) to the catalyzer 7f reclaimed, benzylamine (118mg) and deionized water 7 μ L, react next time. 1HNMR(400MHz,CDCl 3,298K)δ＝7.42–7.28(m,5H),3.98(d,J＝13.2,1H),3.88–3.80(m,3H),3.65–3.52(m,3H),2.61(td,J＝5.4,1.6,1H),1.39(s,3H),1.38(s,3H).MS(EI)m/zcalculated:251.1,found:251.0.
The derivatize of embodiment 19 compound 8
Compound 8 (250mg) is dissolved in 2mL methylene dichloride, adds DMAP (5mg) and acetic anhydride (0.5mL), stirring at room temperature 6 hours.Reaction terminates rear saturated sodium carbonate solution and is neutralized to neutrality, with methylene dichloride and extraction into ethyl acetate, merges organic phase, with the product colorless oil 265mg using column chromatography purification after anhydrous sodium sulfate drying, and productive rate 80%. 1HNMR(400MHz,CDCl 3,298K)δ＝7.36(t,J＝7.3,1H),7.32–7.18(m,4H),5.37–5.22(m,0.7H),5.00–5.01(m,0.45H),4.88(d,J＝15.8,0.45H),4.57–4.41(m,1.2H),4.36–4.08(m,1H),4.00–3.96(m,1H),3.78–3.25(m,4H),2.31(s,1.3H),2.06(s,1.7H),2.02(s,1.7H),1.98(s,1.3H),1.30(s,1.3H),1.28(s,1.7H),1.24(s,1.7H),1.21(s,1.3H).MS(EI)m/zcalculated:335.2,found:334.9.
Persons of ordinary skill in the art may appreciate that the respective embodiments described above realize specific embodiments of the invention, and in actual applications, various change can be done to it in the form and details, and without departing from the spirit and scope of the present invention.

Claims (10)

1. a class chirality polydentate ligand, its structure is as follows, is designated as general formula (I):
Wherein:
X, Y are-O-CH independently of one another, without interfering with each other 2-,-N=CH-or-NH-CH 2-;
W is that phenyl or two ends are connected to A respectively, B two carbon atoms-(CH 2) 4-;
Linker is that carbon carbon is single, double, triple bond directly connects, C 1-8alkyl, to phenyl, a phenyl, adjacent phenyl, Isosorbide-5-Nitrae-divinyl phenyl, ethenylphenyl, ethynyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, Isosorbide-5-Nitrae-methylene radical phenyl or 9,10-anthryl;
R to be carbon number be 1 ~ 12 chain alkyl, carbon number be 5 ~ 7 cyclic alkane base, benzyl or aryl;
Its chirality is by (A a, B a, A, B) order, comprise (R a, R a, R, R), (S a, R a, R, R), (R a, S a, R, R), (R a, R a, S, R), (R a, R a, R, S), (S a, S a, R, R), (S a, R a, S, R), (S a, R a, R, S), (R a, S a, S, R), (R a, S a, R, S), (R a, R a, S, S), (R a, S a, S, S), (S a, R a, S, S), (S a, S a, R, S), (S a, S a, S, R), (S a, S a, S, S).
2. the chiral metal organic coordination polymer that formed of chirality polydentate ligand according to claim 1, its structure is as follows, is designated as general formula (II):
Wherein:
The definition of X, Y, W, R, Linker is all identical with claim 1;
M 1, M 2for transition metal;
Q is assistant ligand;
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion;
N represents the monomer number comprised in metal coordinating polymer, n be more than or equal to 2 natural number.
3. chiral metal organic coordination polymer according to claim 2, is characterized in that, described transition metal is Ag, Au, Cu, Ir, Mn, Mo, Ni, Os, Rh, Ru, Pd, Ti or Zn.
4. chiral metal organic coordination polymer according to claim 2, is characterized in that, described assistant ligand is specially halogen, carbonyl, phenyl ring, luxuriant ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, methyl ethyl diketone negative ion or Phosphine ligands.
5. the preparation method of chiral metal organic coordination polymer according to claim 2, it is characterized in that step for: utilize in the Neo Heliopan AP organic solvent shown in general formula (I) and react with metal precursor, by coordination assembling prepare the chiral metal organic coordination polymer shown in general formula (II);
Its reaction formula is as follows:
6. preparation method according to claim 5, is characterized in that, described metal precursor is MZ aq b, wherein, a be 0,1 or 2, b be 0,1 or 2.
7. a chiral metal organic coordination polymer as claimed in claim 2 application of catalyzer of reacting as asymmetric epoxy addition.
8. the chiral metal organic coordination polymer according to claim 7 application of catalyzer of reacting as asymmetric epoxy addition, it is characterized in that, described chiral metal organic coordination polymer is used for the asymmetric open loop amination reaction of oxirane ring propane derivative and amine.
9. the chiral metal organic coordination polymer according to claim 8 application of catalyzer of reacting as asymmetric epoxy addition, it is characterized in that, described asymmetric open loop amination reaction is used for the preparation of chiral amino alcohol.
10. the chiral metal organic coordination polymer according to claim 7 application of catalyzer of reacting as asymmetric epoxy addition, it is characterized in that, the method of described catalytic applications is: under atmosphere of inert gases, to in the reaction system of reaction substrate, organic solvent and water composition, add described chiral metal organic coordination polymer as catalyzer, stirring heating carries out reacting and obtaining chiral amino alcohol; Wherein, described chiral metal organic coordination polymer catalyzer may be used for catalytic cycle next time after centrifugation.
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