CN105130842B - The metal organic coordination polymer catalyst and its application that novel chiral multidentate ligand, coordination are formed - Google Patents
The metal organic coordination polymer catalyst and its application that novel chiral multidentate ligand, coordination are formed Download PDFInfo
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- 0 C*c(c(C=O)c1)c(C(C)(C)C)cc1C#Cc(ccc1c2-c3c(cccc4)c4ccc3C)cc1ccc2[U]C Chemical compound C*c(c(C=O)c1)c(C(C)(C)C)cc1C#Cc(ccc1c2-c3c(cccc4)c4ccc3C)cc1ccc2[U]C 0.000 description 3
Abstract
The invention belongs to heterogeneous catalysis technical fields, the design and synthesis of a kind of novel chiral multidentate ligand are related to, a kind of novel chiral metal organic coordination polymer and be used as application of the heterogeneous catalysis in asymmetric epoxy addition prepares chiral amino alcohol that this kind of ligand is prepared with metal precursor by Coordinate self-assembly.Chiral metal coordination polymer prepared by chirality multidentate ligand provided by the present invention can be used for being catalyzed asymmetric epoxy addition aminating reaction and prepare chiral amino alcohol to efficiently highly selective.The advantages of this kind of novel self-supported catalyst system and catalyzing combines homogeneous catalysis and heterogeneous catalysis, it is not only able to realize the preparation of chiral amino alcohol under mild conditions, and the catalyst has high efficiente callback and the advantages such as is recycled for multiple times, with good application prospect in terms of preparing chiral amino alcohol using Industrial Catalysis approach.
Description
Technical field
The invention belongs to heterogeneous catalysis technical fields, and in particular to the design of a kind of novel chiral multidentate ligand with
Synthesis, a kind of novel chiral metal organic coordination polymer that this kind of ligand and metal precursor are prepared by Coordinate self-assembly and
As application of the heterogeneous catalysis in asymmetric epoxy addition prepares chiral amino alcohol.
Background technology
Chiral amino alcohol the fields such as organic synthesis, chemical pharmacy, biology, chemical industry all show it is very important effect and
Purposes.Many amino alcohols all have good pharmacological activity, are widely used in medicine, pesticide, biology, chemical industry etc..Simultaneously
Chiral amino alcohol is also a kind of chiral ligand with good coordination ability, is common in each organic micromolecule asymmetry catalysis
In.Therefore there is important theoretical significance and practical application by simply converting the high method for preparing chiral amino alcohol
Value.Wherein chirality 2- amino -1,3, there are two chiral centre, an amino and three hydroxyls for 4- butantriols (ABT) tool, are one
The important C4 organic synthesis segments of kind, can be used for synthesizing a variety of important bioactive molecules, such as Nai Feinawei.
It is that a step builds chiral amino using racemic epoxide propane cheap and easy to get as the asymmetry catalysis ring-opening reaction of raw material
One of common methods of alcohol have many advantages, such as efficient, highly selective, high atom economy, environmentally protective.In recent years with chiral road
The research of Lewis acid catalysis epoxy addition has larger development, especially using titanic as Louis acid catalysis center, with
N,N' ethylene bis (salicylimines) (Salen), 1,1 '-dinaphthols (Binol) etc. take as the catalyst system and catalyzing of chiral ligand
Obtained good result of study.Since this kind of homogeneous catalysis system has many advantages, such as efficient, highly selective, widely closed
Note.It is not allow in product that there are metal residuals, therefore how to recycle catalyst due to the application of amino alcohol in medicine
It avoids metal to the pollution of product and avoids the waste of expensive chiral metal catalyst and achieve the purpose that reuse, always
Since be all that such methods are applied to the major issue that must solve before industrial production.By this kind of organometallic catalytic central loading
It has been reported on to organic polymer, zeolite, ferromagnetic or dendrimer.Although these traditional chiral carrying methods can be in portion
Divide in degree and solve the problems, such as that catalyst recycles, but there is also the catalytic activity compared with homogeneous catalyst and selectivity obviously to drop
It is low, that load capacity is low, uniformity is poor for catalyst load, catalyst easy in inactivation, recovered frequency is relatively low, loads poor repeatability etc. is a series of
The problem of.
Invention content
The present invention is prepared for two kinds of one kind containing Salen and Binol first by the method for transition metal-catalyzed coupling
The bridge ligand of chiral centre.This bridge ligand can efficiently prepare one kind with various metals precursor by way of being coordinated and assembling
Novel both hands self-supported catalyst, to reach chiral by being catalyzed the asymmetry catalysis ring-opening reaction that propylene oxide is raw material
One step of amino alcohol is built and the purpose of catalyst recycling and reuse.Pass through the height of this kind of novel both hands self-supported catalyst
Prepared by effect, be not only able to so that transition metal-catalyzed activated centre is dispersed in metal coordinating polymer, and can be very
The high catalytic activity and selectivity of homogeneous catalyst are kept well.In addition, this kind of coordination polymer type catalyst is common organic molten
Solubility is extremely low in agent and water, can not only realize that product and the efficient of catalyst quickly divide conveniently by the method for filtering
From, and can carry out repeatedly recycling and reuse, to reduce the waste of chiral catalyst, effectively reduce metal to production
The pollution of object meets demand of industrial production.This catalyst can be catalyzed benzylamine to-two ring of 3,5,8- trioxas under mild conditions
The efficient highly selective chiral addition ring-opening reaction of [5,1,0] octane, the product of gained pass through simple deprotection steps, you can
For synthesizing ABT molecules.
There is provided a kind of novel chiral multidentate ligand and its synthetic methods for an object of the present invention.
That it is a further object to provide first stabilities is good, urges that activity is high, selectivity is good, can high efficiente callback and again
The related manufacturing processes of the novel double chiral metal coordination assembling supported catalysts used again.
It is also an object of the present invention to provide a kind of epoxy is catalyzed using this kind of novel both hands self-supported catalyst
The reaction of the chiral open loop of compound.
In order to solve the above technical problems, embodiments of the present invention provide a kind of chiral multidentate ligand, structure is as follows
It is shown, it is denoted as logical formula (I)：
Wherein：
X, Y are each independently, without interfering with each other-O-CH2,-N=CH- or-NH-CH2-；
W is that phenyl or both ends are respectively connected to A, two carbon and nitrogen atoms of B-(CH2)4,；
Linker is that carbon carbon single, double, triple key is directly connected to, C1-8Alkyl, to phenyl, phenyl, adjacent phenyl, Isosorbide-5-Nitrae-two
Ethenylphenyl, ethenylphenyl, ethynyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, Isosorbide-5-Nitrae-methylene phenyl or 9,
10- anthryls；
R be carbon number be 1~12 chain alkyl, carbon number be 5~7 cyclic alkane base, benzyl or aryl；
Its chirality presses (Aa,Ba, A, B) sequence, including (Ra,Ra, R, R), (Sa,Ra, R, R), (Ra,Sa, R, R), (Ra,
Ra, S, R), (Ra,Ra, R, S), (Sa,Sa, R, R), (Sa,Ra, S, R), (Sa,Ra, R, S), (Ra,Sa, S, R), (Ra,Sa, R, S),
(Ra,Ra, S, S), (Ra,Sa, S, S), (Sa,Ra, S, S), (Sa,Sa, R, S), (Sa,Sa, S, R), (Sa,Sa, S, S), structure is as follows
Shown in figure：
Embodiments of the present invention provide the synthetic method of above-mentioned multidentate ligand simultaneously, and the present invention is the 6- by palladium chtalyst
After the coupling reaction coupling of halogenated, methoxy protection BINOL and 4- alkynyl salicylides, remove-insurance in acid condition
Shield, then imines is condensed into achieve the purpose that synthesize both hands bridge ligand with chiral diamine.The Salen- connected with alkynyl
For Binol bridge ligands, synthesis step can simply be indicated such as figure below：
Starting material compound 1 and the like 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,
7577 7586.] synthesize, starting material 2 and the like according to document [H.Michael, W.Marcus, J.Org.Chem.,
2006,71,1825-1836] synthesis.
In basic organic solution, in PdCl2(PPh3)2Under catalysis, alkynyl compounds 1 occurs with bromo compound 2
Sonogashira coupling reactions generate compound 3.Compound 3 sloughs methoxy protecting group under strongly acidic conditions, generates
Compound 4.Compound 4 and the chiral diamine reflux dewatering in organic solution are condensed to form bridge ligand 6.
Embodiments of the present invention provide a kind of preparation method of multiple tooth both hands metal organic coordination polymer simultaneously,
Its structure is as follows, is denoted as logical formula (II)：
Wherein：
M1, M2For transition metal；
X, Y are each independently, without interfering with each other-O-CH2,-N=CH- or-NH-CH2-；
Q is assistant ligand；
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion；
W is that phenyl or both ends are respectively connected to A, two carbon atoms of B-(CH2)4-；
Linker is that carbon carbon single, double, triple key is directly connected to, C1-8Alkyl, to phenyl, phenyl, adjacent phenyl, Isosorbide-5-Nitrae-two
Ethenylphenyl, ethenylphenyl, ethynyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, Isosorbide-5-Nitrae-methylene phenyl or 9,
10- anthryls；
R be carbon number be 1~12 chain alkyl, carbon number be 5~7 cyclic alkane base, benzyl or aryl；
N indicates the monomer number for including in metal coordinating polymer；N is the natural number more than or equal to 2.
Its chirality presses (Aa,Ba, A, B) sequence, including (Ra,Ra, R, R), (Sa,Ra, R, R), (Ra,Sa, R, R), (Ra,
Ra, S, R), (Ra,Ra, R, S), (Sa,Sa, R, R), (Sa,Ra, S, R), (Sa,Ra, R, S), (Ra,Sa, S, R), (Ra,Sa, R, S),
(Ra,Ra, S, S), (Ra,Sa, S, S), (Sa,Ra, S, S), (Sa,Sa, R, S), (Sa,Sa, S, R), (Sa,Sa, S, S), structure is as follows
Shown in figure：
Preferably, in the structure for the multiple tooth metal coordinating polymer that embodiments of the present invention are provided, M1, M2It is represented
Transition metal can be Eu, Au, Cr, Ir, Mn, Mo, Ni, Os, Rh, Ru, Ti, Pd, Y, Yb, La or Zn, assistant ligand can be with
Match for halogen, carbonyl, phenyl ring, luxuriant ring, cyclo-octadiene, hydroxyl, water, carbonate, acetate, acetylacetone,2,4-pentanedione anion or all kinds of phosphines
Body.
The above-mentioned chiral metal organic coordination polymer that embodiments of the present invention are provided, with stability is good, urges work
Property it is high, can high efficiente callback and the advantages that reuse.
Embodiments of the present invention provide the preparation method of above-mentioned chiral metal organic coordination polymer, step simultaneously
For：It is reacted under alkaline condition with metal precursor using chiral multidentate ligand, chiral metal, which is prepared, by coordination assembling has
Machine coordination polymer；
Its reaction equation is as follows：
Wherein：
The coordination polymerization of what embodiments of the present invention were provided the be used to prepare chiral metal organic coordination polymer is anti-
The general formula of Ying Zhong, metal precursor are MZaQb, wherein a 0,1 or 2；B is 0,1 or 2；M, the definition of Z, Q is as hereinbefore.Specifically
For, used metal precursor is preferably in the reaction：Ag2O、AgBF4、AuCl(SMe2)、Cu2O、CuI、Ni(OAc)2、Ti
(Oi-Pr)4、NiCl2、PtCl2、K2PtCl4、CoCl(PPh3)3、CoCl2、FeCl2、MnCl2、ZnCl2、OsH6(t-Bu3P)2、[Ir
(COD)Cl]2、[Ir(COD)OMe]2、IrCl3·3H2O, [IrCp*Cl2]2、Ir(CO)2(acac)、Pd(OAc)2、PdCl2
(CH3CN)2、RuCl3、[Ru(COD)Cl]2、[Ru(p-cymene)Cl2]2、[Ru(benzene)Cl2]2、[Rh(COD)Cl]2Deng.
In addition, the molar ratio of ligand and transition metal is 1:1~1:4, the organic solvent for reacting required can select dichloromethane
Alkane, chloroform, toluene, benzene, tetrahydrofuran, methyl tertiary butyl ether(MTBE), acetonitrile, n,N-Dimethylformamide, n,N-dimethylacetamide,
Methyl pyrrolidone or dimethyl sulfoxide (DMSO) equal solvent；In some cases, the mixed liquor of two to three kinds of above-mentioned organic solvent can be given
Go out better polymerization result.Above-mentioned coordination poly-merization required temperature is generally -50~150 DEG C, and the reaction time is recommended as 1~24
Hour.
Specifically, the laboratory operating procedures of preparation reaction are as follows：At room temperature, match multiple tooth shown in logical formula (I)
Body is dissolved in dichloromethane or other optional solvents, and the dichloromethane of respective metal precursor 1 is added dropwise or other are organic molten
The solution of agent, when solution colour changes, reaction system continues to stir, when TLC is monitored less than ligand, if M1And M2It is same
A kind of metal then reacts stopping；Such as M1And M2For different metals, then continue the dichloromethane that corresponding metal precursor 2 is added dropwise
The solution of alkane or other organic solvents.After sinking to the bottom generation, reaction system continues to stir the regular hour, and reaction stops.It is cold
But it after, is filtered, washed, chiral metal organic coordination polymer shown in logical formula (II) is obtained after vacuum dried.
Through experiment have verified that, chiral metal organic coordination polymer shown in general formula (I), when in its structure linker,
M, in the case that Q, W, X, Y, Z, R, n are various definition described previously herein or substituent group, above-mentioned coordination polymerization can be passed through
Reaction is prepared.
It is anti-as asymmetric epoxy addition that embodiments of the present invention also provide above-mentioned chiral metal organic coordination polymer
The application for the catalyst answered.Further, the method for the catalytic applications is：Under nitrogen atmosphere, to reaction substrate, organic solvent
In the reaction system of water composition, the chiral metal organic coordination polymer is added as catalyst, agitating and heating carries out anti-
It answers, chiral amino alcohol is made；Wherein, reaction substrate is epoxide and level-one amine.In above-mentioned reaction, reaction substrate, water and
The consumption proportion situation of catalyst is：The proportioning of epoxy and amine can be 1~40mmol/mmol, the consumption proportion of organic solvent
Can be 0~15mL/mmol substrates, the consumption proportion of water can be 0~15mL/mmol substrates, and the dosage of catalyst can be 1
×10-3~1mmol/mmol substrates, required temperature are generally 0~80 DEG C, and the reaction time is recommended as 1~96 hour.
Specifically, chiral metal organic coordination polymer catalytic oxidative dehydrogenation embodiments of the present invention provided
The specific operation process that reaction prepares lactic acid is as follows：
Under nitrogen atmosphere, it is organic that the chiral metal that embodiments of the present invention are provided is added into reaction vessel successively
Coordination polymer heats reaction, instead as supported catalyst, reaction substrate, organic solvent and a certain amount of water after stirring evenly
After answering, system is down to room temperature, after being centrifuged with low-speed centrifugal device, supernatant is poured out, the nearly column chromatography of products therefrom is pure
Change separation.The supported catalyst of recycling, it is spare after vacuum dried after organic solvent washing.
Second when recycling, and in the reaction tube containing dry recycling supported catalyst, rejoins reaction substrate, organic
Solvent and a certain amount of water are reacted and are post-processed according to the identical condition of previous reaction.Such circular response 20 times or so,
The selectivity and conversion ratio of reaction are not in how many variation.It can be seen that catalyst provided by the present invention can be well
It realizes recycling and recycles.
To sum up, the present invention is using double Binol of the Salen bridgings of rigidity as a kind of bridging bidentate ligand, suitable
Under the conditions of with metal precursor be coordinated assemble by way of be efficiently prepared a kind of novel both hands self-supported catalyst, to
Realize epoxide asymmetric amine melt ring prepare chiral amino alcohol reaction.This kind of novel both hands self-supported catalyst closes
At simplicity, due to evenly dispersed catalytic active center, very high catalysis being shown in asymmetric epoxy addition and is lived
Property and asymmetry selectivity.It, not only can be in addition, solubility of this kind of coordination polymer type catalyst in common solvents is extremely low
The separation of product and catalyst is easily carried out, and can repeatedly recycle reuse, meets demand of industrial production, effectively drops
Low pollution of the heavy metal to environment.
The both hands metal organic coordination polymer that the present invention designs synthesis is a kind of novel chiral metal organic coordination group
Supported catalyst is filled, can be used for asymmetric epoxy ring opening reaction, efficiently prepare chiral amino alcohol and its derivative.Due to this kind of new
The self-supported catalyst system and catalyzing stability of type is high, does not dissolve in most of organic solvent and water, can be applied to multiclass heterogeneous catalysis
The advantages of reacting, thus combining homogeneous catalysis and heterogeneous catalysis, is not only able to realize chiral amino under mild conditions
The synthesis of alcohol, and with high efficiente callback and the advantage being recycled for multiple times.
Description of the drawings
Fig. 1 is compound 3a prepared in embodiment 11H NMR spectras.
Fig. 2 is compound 3a prepared in embodiment 113C NMR spectras.
Fig. 3 is compound 3b prepared in embodiment 21H NMR spectras.
Fig. 4 is compound 3b prepared in embodiment 213C NMR spectras.
Fig. 5 is compound 4a prepared in embodiment 31H NMR spectras.
Fig. 6 is compound 4a prepared in embodiment 313C NMR spectras.
Fig. 7 is compound 4b prepared in embodiment 41H NMR spectras.
Fig. 8 is compound 4b prepared in embodiment 413C NMR spectras.
Fig. 9 is compound 6a prepared in embodiment 51H NMR spectras.
Figure 10 is compound 6a prepared in embodiment 513C NMR spectras.
Figure 11 is compound 6b prepared in embodiment 61H NMR spectras.
Figure 12 is compound 6b prepared in embodiment 613C NMR spectras.
Figure 13 is the IR spectrograms of compound 7a prepared in embodiment 7.
Figure 14 is the IR spectrograms of compound 7b prepared in embodiment 8.
Figure 15 is the IR spectrograms of compound 7c prepared in embodiment 9.
Figure 16 is the IR spectrograms of compound 7d prepared in embodiment 10.
Figure 17 is the IR spectrograms of compound 7e prepared in embodiment 11.
Figure 18 is the IR spectrograms of compound 7f prepared in embodiment 12.
Figure 19 is the product 8 that chiral self-supported catalysis epoxy ring opening reaction obtains in embodiment 15-181H NMR spectras.
Figure 20 is 19 derivedization of embodiment compound 9 obtained by the reaction1H NMR spectras.
Figure 21 is the HPLC spectrograms of the raceme of the product 9 in embodiment 19.
Figure 22 is the HPLC spectrograms of the derivatization product 9 in embodiment 18.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to each reality of the present invention
The mode of applying is explained in detail.However, it will be understood by those skilled in the art that in each embodiment of the present invention,
In order to make the reader understand this application better, many technical details are proposed.But even if without these technical details and base
In the various changes and modifications of following embodiment, each claim of the application technical side claimed can also be realized
Case.
The preparation of 1 compound 3a of embodiment
N2Under protection, compound 1a (2.2g) is added into dry Schlenk bottles of the 100mL with stirrer successively,
Compound 2 (4.5g), PdCl2(PPh3)2(350mg), PPh3(130mg), triethylamine 10mL and tetrahydrofuran 30mL, room temperature are stirred
It mixes 1 hour.CuI (180mg) is added into this solution again, is heated to 80 DEG C of stirrings for 24 hours, TLC detection compounds 1a disappears, reaction
Stop.Column chromatography obtains product yellow oil 3,2.5g, yield 45% after purification.1H NMR(400MHz,CDCl3, 298K) and 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)
.13C NMR(100MHz,CDCl3, 298K) and 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/z Calcd.for C36H34O6[M-H]+
573.2277；Found:573.2260.[α]D 20=-25 (c 1.0, CHCl3)
The preparation of 2 compound 3b of embodiment
N2Under protection, compound 1b (2.8g) is added into dry Schlenk bottles of the 100mL with stirrer successively,
Compound 2 (4.5g), PdCl2(PPh3)2(350mg), PPh3(130mg), triethylamine 10mL and tetrahydrofuran 30mL, room temperature are stirred
It mixes 1 hour.CuI (180mg) is added into this solution again, is heated to 80 DEG C of stirrings for 24 hours, TLC detection compounds 1b disappears, reaction
Stop.Column chromatography after purification product yellow oil 3b, 5.2g, yield 88%.1H NMR(400MHz,CDCl3) 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).13C NMR(101MHz,CDCl3) 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 (c 1.0, CHCl3)
The preparation of 3 compound 4a of embodiment：
Compound 3a (574mg), chloroform 15mL and methanol 3mL are added in 50mL round-bottomed flasks, forms the solution of yellow.
The hydrochloric acid (3.5mL) of 6M is added, is stirred at room temperature 6 hours, TLC detects raw material compound 3a and disappears.Stop reaction, with 10% carbonic acid
Sodium solution is neutralized to neutrality, liquid separation.Water phase dichloromethane extracts three times, merges organic phase, after being dried with anhydrous sodium sulfate, column
After chromatographic purifying product yellow solid 4a, 480mg, yield 98%.1H NMR(400MHz,CDCl3, 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)13C NMR(100MHz,CDCl3, 298K) and 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/z Calcd.for
C36H34O6[M-H]573.2277；Found:573.2260.[α]D 20=+22 (c 1.0, CHCl3)
The preparation of 4 compound 4b of embodiment：
Compound 3b (650mg), chloroform 15mL and methanol 3mL are added in 50mL round-bottomed flasks, forms the solution of yellow.
The hydrochloric acid (3.5mL) of 6M is added, is stirred at room temperature 6 hours, TLC detects raw material compound 3b and disappears.Stop reaction, with 10% carbonic acid
Sodium solution is neutralized to neutrality, liquid separation.Water phase dichloromethane extracts three times, merges organic phase, after being dried with anhydrous sodium sulfate, column
After chromatographic purifying product yellow solid 4b, 550mg, yield 98%.1H NMR(400MHz,CDCl3, 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)13C NMR(101MHz,
DMSO-D6, 298K) and 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/z Calcd.for C39H31O4[M+H]+
563.2222；Found:563.2211.[α]D 20=+183 (c 1.0, CHCl3)
The preparation of 5 compound 6a of embodiment：
In the round-bottomed flask dried to 50mL, compound 4a (486mg), compound 5 (106mg) and methanol 10mL is added.
It is heated to return stirring 2 hours, TLC detects raw material and disappears, and stops reaction, is cooled to room temperature, and it is yellow that column chromatography obtains product after purification
Color solid 6,570mg, 97%.1H NMR(400MHz,CDCl3, 298K) and 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).13C NMR(101MHz,CDCl3, 298K) and 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 (c 1.0, CHCl3)
.HRMS(ESI/TOF)M/z Calcd.for C80H65N2O6[M+H]+1149.4843；Found:1149.4832
The preparation of 6 compound 6c of embodiment：
In the round-bottomed flask dried to 50mL, compound 4b (486mg), compound 5 (106mg) and methanol 10mL is added.
It is heated to return stirring 2 to disappear, TLC detects raw material and disappears, and stops reaction, is cooled to room temperature, and it is yellow that column chromatography obtains product after purification
Color solid 6c, 570mg, 97%.
The preparation of 7 both hands self-supported catalyst 7a of embodiment：
Under nitrogen atmosphere protection, addition ligand 6a (114mg) and anhydrous dichloromethane into Schlenk bottle of 25mL successively
Alkane 5mL is stirred at room temperature 5 minutes.The dichloromethane solution of 0.5M Ti (Oi-Pr) 4 is added dropwise into this yellow solution
(0.4mL) has Chinese red Precipitation.Continue to be stirred at room temperature 12 hours after being added dropwise, deionized water (0.14mL) be added,
Continue stirring 12 hours, filtering, precipitation is washed with dichloromethane.Obtained solid is vacuum dried, obtains Chinese red solid 127mg,
Yield 99%.IR(KBr pellet)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.elemental analysis calcd (%) for
(C80H58N2O6Ti2·1.5CH2Cl2)n:C,71.64；H,4.50；N,2.05；found:C 71.92,H 4.74,N,2.04.
The preparation of 8 both hands self-supported catalyst 7b of embodiment：
Under nitrogen atmosphere protection, addition ligand 6b (114mg) and anhydrous dichloromethane into Schlenk bottle of 25mL successively
Alkane 5mL is stirred at room temperature 5 minutes.The dichloromethane solution of 0.5M Ti (Oi-Pr) 4 is added dropwise into this yellow solution
(0.4mL) has Chinese red Precipitation.Continue to be stirred at room temperature 12 hours after being added dropwise, deionized water (0.14mL) be added,
Continue stirring 12 hours, filtering, precipitation is washed with dichloromethane.Obtained solid is vacuum dried, obtains Chinese red solid 127mg,
Yield 99%.IR(KBr pellet)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；Elemental analysis calcd (%) for (C80H60N2O6Ti2·1.5CH2Cl2)n:C,
71.53,H,4.64,N,2.05；
The preparation of 9 both hands self-supported catalyst 7c of embodiment：
Under nitrogen atmosphere protection, addition ligand 6c (130mg) and anhydrous dichloromethane into Schlenk bottle of 25mL successively
Alkane 5mL is stirred at room temperature 5 minutes.The dichloromethane solution of 0.5M Ti (Oi-Pr) 4 is added dropwise into this yellow solution
(0.4mL) has Chinese red Precipitation.Continue to be stirred at room temperature 12 hours after being added dropwise, deionized water (0.14mL) be added,
Continue stirring 12 hours, filtering, precipitation is washed with dichloromethane.Obtained solid is vacuum dried, obtains Chinese red solid 142mg,
Yield 99%.IR(KBr pellet)ν3444.63,2954.09,2348.97,1614.33,1462.46,1384.47,
1342.26,1243.74,668.24,526.18cm-1；Elemental analysis calcd (%) for
(C92H66N2O6Ti2·1.5CH2Cl2)n:C,73.95；H,4.58；N,1.84；found:C 73.71,H 4.73,N,1.80.
The preparation of 10 both hands self-supported catalyst 7d of embodiment：
Under nitrogen atmosphere protection, addition ligand 6d (130mg) and anhydrous dichloromethane into Schlenk bottle of 25mL successively
Alkane 5mL is stirred at room temperature 5 minutes.The dichloromethane solution of 0.5M Ti (Oi-Pr) 4 is added dropwise into this yellow solution
(0.4mL) has Chinese red Precipitation.Continue to be stirred at room temperature 12 hours after being added dropwise, deionized water (0.14mL) be added,
Continue stirring 12 hours, filtering, precipitation is washed with dichloromethane.Obtained solid is vacuum dried, obtains Chinese red solid 142mg,
Yield 99%.IR(KBr pellet)ν3448.92,2348.83,1618.66,1459.75,1242.00,818.24,
579.63,cm-1；Elemental analysis calcd (%) for (C92H68N2O6Ti2·1.5CH2Cl2)n:C,73.85；H,
4.71；N,1.84；found:C 73.67,H 4.97,N,1.69.
The preparation of 11 both hands self-supported catalyst 7e of embodiment：
Under nitrogen atmosphere protection, addition ligand 6e (130mg) and anhydrous dichloromethane into Schlenk bottle of 25mL successively
Alkane 5mL is stirred at room temperature 5 minutes.The dichloromethane solution of 0.5M Ti (Oi-Pr) 4 is added dropwise into this yellow solution
(0.4mL) has Chinese red Precipitation.Continue to be stirred at room temperature 12 hours after being added dropwise, deionized water (0.14mL) be added,
Continue stirring 12 hours, filtering, precipitation is washed with dichloromethane.Obtained solid is vacuum dried, obtains Chinese red solid 142mg,
Yield 99%.IR(KBr pellet)ν3448.92,2348.83,1618.66,1459.75,1242.00,818.24,
579.63,cm-1；Elemental analysis calcd (%) for (C92H68N2O6Ti2·1.5CH2Cl2)n:C,73.85；H,
4.71；N,1.84；found:C 73.67,H 4.97,N,1.69.
The preparation of 12 both hands self-supported catalyst 7f of embodiment：
Ligand 6e (130mg) is added into Schlenk bottles of 25mL successively and absolute ethyl alcohol 5mL is stirred at room temperature 5 minutes.To
Mn (OAc) is once added in this yellow solution2·4H2The rapid blackening of O (50mg) solution colour.It is cooling after return stirring 1 hour
To room temperature, LiCl (21mg) is once added, continues return stirring 1 hour under air.Be cooled to room temperature, into this dark solution by
It is added dropwise to the dichloromethane solution (0.4mL) of 0.5M Ti (Oi-Pr) 4, there is Precipitation.Continue to stir in room temperature after being added dropwise
After mixing 12 hours, deionized water (0.14mL) is added, continues stirring 12 hours, filtering, precipitation is washed with dichloromethane.Gained is solid
Body is vacuum dried, obtains brown solid 145mg, yield 99%.IR(KBr pellet)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.elemental analysis calcd (%) for
(C92H68ClMnN2O7Ti·3CH2Cl2)n:C,66.86；H,4.37；N,1.64；found:C 66.78,H 4.77,N,1.78.
The novel double chiral metal organic coordination assembling supported catalyst 7a of embodiment 13 are for being catalyzed asymmetric epoxy addition
It amination and recycles
Under nitrogen atmosphere protection, catalyst 7a, dry toluene 0.5mL, compound 8 is added into 25mL centrifuge tubes successively
(144mg), 7 μ L of benzylamine (118mg) and deionized water.18h is reacted in 40 DEG C of heating stirrings, is cooled to room temperature, 6mL ether is added
After centrifuge out supernatant liquor, with ether wash precipitation three times, catalyst precipitation it is vacuum dried after it is spare.Merge organic
Phase, column chromatography for separation go out product colorless oil 250mg, yield 99%.It is surveyed with HPLC after derivatization in the way of embodiment 19
Its fixed optical purity is ee=89%.It is added dry toluene 0.5mL again to the catalyst 7a of recycling, compound 8 (144mg),
7 μ L of benzylamine (118mg) and deionized water, carry out next secondary response.1H NMR(400MHz,CDCl3, 298K) and 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/z calculated:251.1,found:251.0.
The novel double chiral metal organic coordination assembling supported catalyst 7b of embodiment 14 are for being catalyzed asymmetric epoxy addition
It amination and recycles
Under nitrogen atmosphere protection, catalyst 7b, dry toluene 0.5mL, compound 8 is added into 25mL centrifuge tubes successively
(144mg), 7 μ L of benzylamine (118mg) and deionized water.18h is reacted in 40 DEG C of heating stirrings, is cooled to room temperature, 6mL ether is added
After centrifuge out supernatant liquor, with ether wash precipitation three times, catalyst precipitation it is vacuum dried after it is spare.Merge organic
Phase, column chromatography for separation go out product colorless oil 250mg, yield 99%.It is surveyed with HPLC after derivatization in the way of embodiment 19
Its fixed optical purity is ee=91%.It is added dry toluene 0.5mL again to the catalyst 7b of recycling, compound 8 (144mg),
7 μ L of benzylamine (118mg) and deionized water, carry out next secondary response.1H NMR(400MHz,CDCl3, 298K) and 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/z calculated:251.1,found:251.0.
The novel double chiral metal organic coordination assembling supported catalyst 7c of embodiment 15 are for being catalyzed asymmetric epoxy addition
It amination and recycles
Under nitrogen atmosphere protection, catalyst 7c, dry toluene 0.5mL, compound 8 is added into 25mL centrifuge tubes successively
(144mg), 7 μ L of benzylamine (118mg) and deionized water.18h is reacted in 40 DEG C of heating stirrings, is cooled to room temperature, 6mL ether is added
After centrifuge out supernatant liquor, with ether wash precipitation three times, catalyst precipitation it is vacuum dried after it is spare.Merge organic
Phase, column chromatography for separation go out product colorless oil 250mg, yield 99%.It is surveyed with HPLC after derivatization in the way of embodiment 19
Its fixed optical purity is ee=93%.It is added dry toluene 0.5mL again to the catalyst 7c of recycling, compound 8 (144mg),
7 μ L of benzylamine (118mg) and deionized water, carry out next secondary response.1H NMR(400MHz,CDCl3, 298K) and 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/z calculated:251.1,found:251.0.
The novel double chiral metal organic coordination assembling supported catalyst 7d of embodiment 16 are for being catalyzed asymmetric epoxy addition
It amination and recycles
Under nitrogen atmosphere protection, catalyst 7d, dry toluene 0.5mL, compound 8 is added into 25mL centrifuge tubes successively
(144mg), 7 μ L of benzylamine (118mg) and deionized water.18h is reacted in 40 DEG C of heating stirrings, is cooled to room temperature, 6mL ether is added
After centrifuge out supernatant liquor, with ether wash precipitation three times, catalyst precipitation it is vacuum dried after it is spare.Merge organic
Phase, column chromatography for separation go out product colorless oil 250mg, yield 99%.It is surveyed with HPLC after derivatization in the way of embodiment 19
Its fixed optical purity is ee=93%.It is added dry toluene 0.5mL again to the catalyst 7d of recycling, compound 8 (144mg),
7 μ L of benzylamine (118mg) and deionized water, carry out next secondary response.1H NMR(400MHz,CDCl3, 298K) and 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/z calculated:251.1,found:251.0.
The novel double chiral metal organic coordination assembling supported catalyst 7e of embodiment 17 are for being catalyzed asymmetric epoxy addition
It amination and recycles
Under nitrogen atmosphere protection, catalyst 7e, dry toluene 0.5mL, compound 8 is added into 25mL centrifuge tubes successively
(144mg), 7 μ L of benzylamine (118mg) and deionized water.18h is reacted in 40 DEG C of heating stirrings, is cooled to room temperature, 6mL ether is added
After centrifuge out supernatant liquor, with ether wash precipitation three times, catalyst precipitation it is vacuum dried after it is spare.Merge organic
Phase, column chromatography for separation go out product colorless oil 250mg, yield 99%.It is surveyed with HPLC after derivatization in the way of embodiment 19
Its fixed optical purity is ee=67%.It is added dry toluene 0.5mL again to the catalyst 7e of recycling, compound 8 (144mg),
7 μ L of benzylamine (118mg) and deionized water, carry out next secondary response.1H NMR(400MHz,CDCl3, 298K) and 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/z calculated:251.1,found:251.0.
The novel double chiral metal organic coordination assembling supported catalyst 7f of embodiment 18 are for being catalyzed asymmetric epoxy addition
It amination and recycles
Under nitrogen atmosphere protection, catalyst 7f, dry toluene 0.5mL, compound 8 is added into 25mL centrifuge tubes successively
(144mg), 7 μ L of benzylamine (118mg) and deionized water.18h is reacted in 40 DEG C of heating stirrings, is cooled to room temperature, 6mL ether is added
After centrifuge out supernatant liquor, with ether wash precipitation three times, catalyst precipitation it is vacuum dried after it is spare.Merge organic
Phase, column chromatography for separation go out product colorless oil 250mg, yield 55%.It is surveyed with HPLC after derivatization in the way of embodiment 19
Its fixed optical purity is ee=85%.It is added dry toluene 0.5mL again to the catalyst 7f of recycling, compound 8 (144mg),
7 μ L of benzylamine (118mg) and deionized water, carry out next secondary response.1H NMR(400MHz,CDCl3, 298K) and 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/z calculated:251.1,found:251.0.
The derivatization of 19 compound 8 of embodiment
Compound 8 (250mg) is dissolved in 2mL dichloromethane, DMAP (5mg) and acetic anhydride (0.5mL) is added, room temperature is stirred
It mixes 6 hours.It is neutralized to neutrality with saturated sodium carbonate solution after reaction, is extracted, is associated with dichloromethane and ethyl acetate
Machine phase uses column chromatography the product colorless oil 265mg of purification, yield 80% after being dried with anhydrous sodium sulfate.1H NMR
(400MHz,CDCl3, 298K) and 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/z
calculated:335.2,found:334.9.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (7)
1. a kind of chirality multidentate ligand, structure is as follows, is denoted as logical formula (I)：
Wherein：
X, Y are each independently, without interfering with each other-N=CH- or-NH-CH2-；
W is that phenyl or both ends are respectively connected to A, two carbon atoms of B-(CH2)4-；
Linker be-CH=CH- ,-C ≡ C-, to phenyl, phenyl, adjacent phenyl, 1,4- divinyl phenyl, ethenylphenyl,
Ethynyl phenyl, 1,4- diacetylenes phenyl, xenyl, 1,4- methylene phenyl or 9,10- anthryls；
R be carbon number be 1~12 chain alkyl, carbon number be 5~7 cyclic alkane base or benzyl；
Its chirality presses (Aa,Ba, A, B) sequence, be (Ra,Ra, R, R), (Sa,Ra, R, R), (Ra,Sa, R, R), (Ra,Ra, S, R),
(Ra,Ra, R, S), (Sa,Sa, R, R), (Sa,Ra, S, R), (Sa,Ra, R, S), (Ra,Sa, S, R), (Ra,Sa, R, S), (Ra,Ra,S,
S), (Ra,Sa, S, S), (Sa,Ra, S, S), (Sa,Sa, R, S), (Sa,Sa, S, R), (Sa,Sa,S,S)。
2. a kind of chiral multidentate ligand according to claim 1 is formed by chiral metal organic coordination polymer, structure is such as
Shown in lower, it is denoted as logical formula (II)：
Wherein：
X, the definition of Y, W, R, Linker are identical as claim 1；
M1, M2For Mn or Ti；
Q is assistant ligand；
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion；
N indicates that the monomer number for including in metal coordinating polymer, n are the natural number more than or equal to 2.
3. chiral metal organic coordination polymer according to claim 2, which is characterized in that the assistant ligand is specially
Halogen, carbonyl, cyclo-octadiene, hydroxyl, water, carbonate, acetate or acetylacetone,2,4-pentanedione anion.
4. the preparation method of the chiral metal organic coordination polymer described in claim 2, it is characterised in that step is：Using logical
It reacts with the metal precursor of Mn or Ti shown in formula (I), is prepared shown in logical formula (II) by being coordinated assembling in organic solvent
Chiral metal organic coordination polymer；
Its reaction equation is as follows：
The metal precursor is MZaQb, wherein a 0,1 or 2, b 0,1 or 2.
5. a kind of chiral metal organic coordination polymer as claimed in claim 2 is as meso 3,5,8- trioxa-l-phosphabicyclos
[5,1,0] application of the catalyst of the asymmetric epoxy addition aminating reaction of pungent alkyl compound.
6. chiral metal organic coordination polymer according to claim 5 is urged as asymmetric epoxy addition aminating reaction
The application of agent, which is characterized in that the asymmetry open loop aminating reaction is used for the preparation of chiral amino alcohol.
7. chiral metal organic coordination polymer according to claim 5 is urged as asymmetric epoxy addition aminating reaction
The application of agent, which is characterized in that the method for the catalytic applications is：Under atmosphere of inert gases, to reaction substrate, You Jirong
In the reaction system of agent and water composition, the chiral metal organic coordination polymer is added as catalyst, agitating and heating carries out
It reacts and chiral amino alcohol is made；Wherein, the chiral metal organic coordination polymer catalyst can be with after centrifugation
For catalytic cycle next time.
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