CN1579627A - Chiral ligand metal complex catalyst system, and its preparation method and use - Google Patents
Chiral ligand metal complex catalyst system, and its preparation method and use Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0269—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry
- B01J2531/0272—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry derived from carbohydrates, including e.g. tartrates or DIOP
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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Abstract
The invention relates to chirality phosphine ligand metal complex catalyse system, which is composed by complex formed by ligand and metal Rh, Ru, Ir, Pt or Pd or ligand and metal precursor in of 1-2 mol ratio. The phosphine ligand is a kind of effective chirality phosphate ligand composed by D-mannitol or L-mannitol after reaction. The catalyst composed by the chirality ligand and rhodium metallic compound in asymmetry hydrogenation reaction can work in room temperature. With a wide applied range, catalyst's activation and stereoselectivity is not influenced from normal pressure to high pressure. Reaction time is 1-24 hours. Mol ratio of ligand and metal rhodium compound is 1:1-2:1. Ratio of reactant and catalyst is 100-10,000.
Description
Technical field
The present invention relates to a kind of chiral ligand metal complex to catalyze system;
The invention still further relates to the preparation method of above-mentioned catalyst system and catalyzing;
The invention still further relates to the application of above-mentioned catalyst system and catalyzing in asymmetric hydrogenation.
Background technology
The catalysis asymmetric hydrogenation is the core technology in the asymmetric syntheses, is one of most effectual way of synthesizing optical homochiral medicine, agricultural chemicals, food additives, spices, and the design of chiral ligand synthetic be the key factor that realizes this core technology.At present, existing many chirality bidentate phosphine ligandses are developed by people in succession, but because the synthetic difficulty of most parts is big, poor stability, synthetic costing an arm and a leg is difficult to be applied in the industrial production, and therefore real to be successfully applied to industrial chiral phosphine ligand few.The DIPAMP that U.S. Monsanto Company is only arranged that is used for commercial Application of present bibliographical information, several classes that the BINAP of Japanese high sand spices etc. are very few.Recently, monodentate chirality phosphite ester, phosphoramidite class part are also developed by people in succession, though this type of part is synthetic easy, Stability Analysis of Structures, but the chiral induction ability of this type of part, the ligand substrate scope of application is narrow, has also limited it in industrial application.
Summary of the invention
The object of the present invention is to provide a kind of chiral ligand metal complex to catalyze system;
Another purpose of the present invention is to provide the preparation method of above-mentioned catalyst system and catalyzing, specifically the preparation method of part in the catalyst system and catalyzing.
Chiral ligand metal complex to catalyze system provided by the invention, the system that complex compound that is formed by part and metal Rh, Ru, Ir, Pt or Pd or part and respective metal precursor are formed by 1～2 mol ratio; Wherein part has following structure and structural formula title:
Or
Wherein, the R in the part
1, R
2Group is: the C of hydrogen, phenyl, substituted-phenyl, 1-naphthyl or 2-naphthyl
6-C
60In contain N, S, O, P or do not contain the aromatic group of N, S, O, P; The C of methyl, ethyl, propyl group or butyl
1～C
40The interior fat group that contains N, S, O, P;
In the part
Group is:
Wherein: R=HR=CH3R=Ph
Wherein: R1=CH3 R2=HR1=CH3 R2=CH3R1=OCH3 R2=HR1=OCH
3R2=CH3
Wherein: R1=CH3 R2=H, R2=CH3 R1=H, R1=CH3 R2=CH3, R1=Ph R2=H, R1=OCH3 R2=H, R2=OCH3 R1=H, R1=OCH
3R2=CH3, R2=OCH
3R1=CH3, R1=t-Bu R2=t-Bu, R1=Si (
CH
3) 3 R2=H, R1=t-Bu R2=H, R2=t-Bu R1=H,
The present invention prepares the method for part in the above-mentioned catalyst system and catalyzing, is that chiral source is synthesized a kind of phosphite ester ligand of chirality efficiently through three-step reaction with D-type sweet mellow wine or L-type sweet mellow wine, and the structure of part and synthetic technology route are as follows:
Or
Wherein:
In the first step reaction, aldehyde: sweet mellow wine: the concentrated sulfuric acid (mol ratio) is 1: 4.4: 2;
In the reaction of second step, material (1): NaH: RX (mol ratio)=l: 1: 1.1;
In the three-step reaction, material (2): diphenol: PCl
3: EtZ
3N (mol ratio)=1: 1.2: 1: 2.2.
Specifically, the preparation process of part is in the catalyst system and catalyzing:
A) aldehyde in molar ratio: sweet mellow wine: the concentrated sulfuric acid is 1: 4.4: 2, join in the solvent DMF that equates with above-mentioned cumulative volume, reaction is 10-80 hour under the stirring at room, the reactant mixture filtration is obtained solid and uses petroleum ether, the solids chloroform extracting of boiling, the solids that filtration obtains is through recrystallizing methanol;
B) solids that step 1 is obtained, sodium hydride and halogenated aliphatic hydrocarbon are to join in DMF at 1: 1: 1.1 in molar ratio, under the room temperature stirring reaction 0.5-3 hour, reactant mixture extracted with diethyl ether, saline solution washing, anhydrous sodium sulfate drying is removed solvent and is obtained solids;
C) under the nitrogen protection, will poly-2 solids that obtain of step drip triethylamine in 0-5 ℃, dropwise the back, add diphenol again under room temperature stirring reaction 1-3 hour, filter, remove solvent and obtain required part through the ether recrystallization stirring at room reaction 5-30 minute; Mol ratio in this step is a solids: diphenol: phosphorus trichloride (PCl
3): triethylamine=1: 1.2: l: 2.2.
Aldehyde used among described preparation method's step a is C
1-C
60Fatty aldehyde or C
6-C
30Aromatic aldehyde;
Used aldehyde is formaldehyde, acetaldehyde or benzaldehyde among described preparation method's step a.
Used halogenated aliphatic hydrocarbon is that iodomethane, aromatic hydrocarbons replace halogenated methyl, aromatic hydrocarbons replaces halogenated methylene or aromatic hydrocarbons replaces the halo methine among described preparation method's step b.
Used diphenol is 2 among described preparation method's step c, 2 '-dinaphthalene diphenol, 3,2 of 3 ' replacement, 2 '-dinaphthalene diphenol, 2,2 of 2 '-'-biphenyl diphenol or replacement, 2 '-'-biphenyl diphenol.
Chiral phosphine ligand ManniPhos of the present invention and metal precursor original position form metal complex the hydrogenation of C=C key, C=N key, C=O key is had high catalytic activity and optical selective.Be reflected at 1-100atm, carry out under-20～200 ℃ the temperature, can select the alcohols solvent of protic for use, also can select the C of non-proton property according to raw material types
6～C
10Alkane, CH
2Cl
2, CH
2ClCH
2Cl, CH
3Cl, CCl
4, oxolane etc. makes solvent.
The invention effect
It is applied widely that the present invention designs the catalyst that synthetic chiral ligand ManniPhos and rhodium metal compound form, and can be applied to the asymmetric hydrogenation of the two keys of multiclass C=C.ManniPhos and [Rh (COD)
2] BF
4The catalyst that forms under the condition is mainly used in following a few class substrate catalysis asymmetry hydrogenation reaction in position:
(1) catalysis asymmetry hydrogenation reaction of α-dehydroamino acid;
(2) catalysis asymmetry hydrogenation reaction of β-dehydroamino acid;
(3) catalysis asymmetry hydrogenation reaction of the itaconic acid compounds of itaconic acid and β-replacement thereof;
(4) catalysis asymmetry hydrogenation reaction of alpha-substituted non-annularity and ring-type enamine.
The chiral ligand ManniPhos of the present invention's design is to air-stable, easy operating, preservation; The part synthesis route is simple, need not high temperature in the building-up process, violent operating condition such as high pressure; Part is synthetic with low cost, and synthesis material sweet mellow wine, aldehyde, phosphorus trichloride etc. cheaply are easy to get.The catalyst stereoselectivity height that ManniPhos and rhodium metal compound form, enantio-selectivity all can be up to 99.9% for above four class substrates; The catalyst activity height that ManniPhos and rhodium metal compound form, TON can be up to 10,000.
The present invention designs the asymmetric hydrogenation mild condition of the catalyst participation of synthetic chiral ligand ManniPhos and the formation of rhodium metal compound, can at room temperature react; The force applications scope of hydrogen is wide, does not all influence activity of such catalysts from the normal pressure to the high pressure, stereoselectivity, and the reaction time is 1～24 hour, and the mol ratio of part and metal rhodium compound is 1: 1～4: 1, and reaction substrate is 100～10,000 with the ratio of catalyst.
Chiral monophosphorus ligand ManniPhos proposed by the invention has characteristics such as synthetic route is simple, cost is low, stable in the air, and its metal Rh, Ru, Ir, Pd, Pt complex compound have high catalytic activity and optical selective to the hydrogenation reaction of C=C, C=O, C=N key.The catalyst that chiral ligand and rhodium metal compound form has high catalytic activity and stereoselectivity to the itaconic acid four class substrates of α-dehydroamino acid, β-dehydroamino acid, itaconic acid and β-replacement thereof, in temperature is 0～100 ℃, under the reaction condition of pressure 1～100atm, TON can be up to 10,000, enantio-selectivity can be up to 99.9%.Use this chiral ligand, can prepare polytype quiral products such as chiral drug, chirality agricultural chemicals, chiral amino acid by asymmetric hydrogenation, have important use in industries such as medicine, agricultural chemicals, spices, food and feed additives and be worth.
By comparison, though the monodentate phosphine ligand of existing Reetz etc. is synthetic fairly simple, the chemical property of part is stable, in air, can stablize and deposit, but a Rh complex compound activity to the itaconic acid analog derivative, enantioselectivity be (S/C=5000 better, e.e=99.6%), but to α-dehydroamino acid, eneamines, the β-activity of dehydroamino acids substrate, enantioselectivity is relatively poor or extreme difference.
The specific embodiment
(1) part is synthetic
Embodiment 1
Add the concentrated sulfuric acid (20ml) in the churned mechanically there-necked flask in having of 1000ml, D-sweet mellow wine (100g), benzaldehyde (120ml) and solvent DMF (300ml), this reactant mixture is after stirring at room is reacted 3 days, reactant mixture poured in the frozen water that contains 30 gram potash and 500ml benzinums into vigorous stirring up to ice-out, filtration obtains solid and uses petroleum ether, solids is with the chloroform extracting of 400ml boiling 2 times, the solids that filtration obtains can obtain product white solid 1 (86g, 42%) through recrystallizing methanol.
In the round-bottomed flask of a 250ml, add sodium hydride (12mmol, the sodium hydride that is melted into mineral oil of content 80%), last synthetic compound 1 (10mmol) of step, solvent DMF (40ml), at room temperature stirring reaction is after 1 hour with this reactant mixture, and adding iodomethane (10mmol) continues at room temperature to react 1 hour.Reactant mixture is with 20ml water dilution extracted with diethyl ether, the salt water washing of being satiated with food, anhydrous sodium sulfate drying is removed solvent through decompression and is obtained solids, through carrene/n-hexane be recrystallized white crystal 2 (3.54g, 95%).
Under nitrogen protection; have to add in the there-necked flask of dropping funel and stirring to 100ml and go up step synthetic compound (5mmol); drip phosphorus trichloride (5mmol) down at 0 ℃; dropwise that the recession deicing is bathed and in the stirring at room reaction after 1 hour; add triethylamine (15.5mmol) down in 0 ℃; dropwise that the recession deicing is bathed and stirring at room reaction 15 minutes, 2 of solid R type, 2 '-dinaphthalene diphenol (R-BINOL) joined in the reactant mixture under room temperature stirring reaction 1～3 hour.Add the ether dilution and help filter, remove solvent through decompression and obtain the foam-like solids, obtain white solid through the ether recrystallization and be required part (2.74g, 80%) with diatomite.
(2) catalysis asymmetry hydrogenation reaction
Embodiment 1
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, hydrogenation reaction substrate 2-acetamidoacrylic acid methyl esters (0.5mmol) is transferred in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep synthesis under normal pressure cessation reaction after 30 minutes, filter with short silicagel column, to filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get S-acetylamino methyl propionate yield 100% (in 2-acetamidoacrylic acid methyl esters), enantiomeric excess is 97.7%ee.
Embodiment 2
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, hydrogenation reaction substrate 2-acetylamino methyl cinnamate (0.5mmol) is transferred in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep synthesis under normal pressure cessation reaction after 30 minutes, filter with short silicagel column, to filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get S-acetylamino methyl phenylpropionate yield 100% (in 2-acetylamino methyl cinnamate), enantiomeric excess is 98.0%ee.
Embodiment 3
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, the precursor (0.5mmol) of hydrogenation reaction substrate DOPA is transferred in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep synthesis under normal pressure cessation reaction after 30 minutes, filter with short silicagel column, to filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get L-DOPA yield 100% (in the precursor of DOPA), enantiomeric excess is 98.0%ee.
Embodiment 4
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, hydrogenation reaction substrate dimethyl itaconate (0.5mmol) is transferred in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep synthesis under normal pressure cessation reaction after 3 hours, filter with short silicagel column, to filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get (R)-2-dimethyl succinic acid dimethyl ester 100% (in dimethyl itaconate), enantiomeric excess is 99.0%ee.
Embodiment 5
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, catalyst is transferred in the reactor, hydrogenation reaction substrate dimethyl itaconate (0.5mmol) joins in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep 10 kilograms of stress reactions cessation reaction after 3 hours, filter with short silicagel column, will filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get (R)-2-dimethyl succinic acid dimethyl ester 100% (in dimethyl itaconate), enantiomeric excess is 98.8%ee.
Embodiment 6
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, catalyst is transferred in the reactor, hydrogenation reaction substrate 2-acetylaminohydroxyphenylarsonic acid 2-M Cr (0.5mmol) joins in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep 40 kilograms of stress reactions cessation reaction after 24 hours, filter with short silicagel column, to filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get (S)-2-acetylaminohydroxyphenylarsonic acid 2-methyl butyrate 100% (in 2-acetylaminohydroxyphenylarsonic acid 2-M Cr), enantiomeric excess is 99.1%ee.
Embodiment 7
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, catalyst is transferred in the reactor, hydrogenation reaction substrate acetylamino styrene (0.5mmol) joins in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep 10 kilograms of stress reactions cessation reaction after 3 hours, filter with short silicagel column, will filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get (S)-acetylamino vinylbenzene 100% (in acetylamino styrene), enantiomeric excess is 99.8%ee.
Embodiment 8
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, hydrogenation reaction substrate 2-acetylamino styrene (0.5mmol) is transferred in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep synthesis under normal pressure cessation reaction after 3 hours, filter with short silicagel column, to filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get (S)-acetylamino vinylbenzene 100% (in 2-acetylamino styrene), enantiomeric excess is 99.8%ee.
Embodiment 9
Under nitrogen protection, 2.0mg (0.005mmol) [Rh (COD)
2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, catalyst is transferred in the reactor, hydrogenation reaction substrate acetylamino styrene (50mmol) and 20ml solvent join in this reactor, continue to feed hydrogen behind the hydrogen exchange 3 times, keep 10 kilograms of stress reactions cessation reaction after 6 hours, filter with short silicagel column, will filter after gained filtrate concentrates, carry out content and optical purity mensuration with GC, get (S)-acetylamino vinylbenzene 100% (in acetylamino styrene), enantiomeric excess is 96.0%ee.
Embodiment 10
Under nitrogen protection, 2.0mg (0.005mmol) [Ir (COD) 2] BF
4With above-mentioned synthetic chiral ligand ManniPhos (0.010mmol), methylene chloride (1ml) is at room temperature in the reactor of 10ml, react and made catalyst in 10-30 minute, catalyst is transferred in the reactor, hydrogenation reaction substrate phenylpropyl alcohol azomethine (0.5mmol) and 2ml solvent join in this reactor, continue behind the hydrogen exchange 3 times to feed hydrogen, keep 60 kilograms of stress reactions cessation reaction after 6 hours.Filter with short silicagel column, will filter after gained filtrate concentrates, carry out content and optical purity is measured with GC, get Phenpromethamine yield 100% (in the phenylpropyl alcohol azomethine), enantiomeric excess is 98.0%ee.
Embodiment 11
Under nitrogen protection; 2.0mg (0.005mmol) phellandrene ruthenic chloride; with above-mentioned synthetic chiral ligand ManniPhos (0.010mmol); methylene chloride (1ml) is at room temperature in the reactor of 10ml; react and made catalyst in 10-30 minute; catalyst is transferred in the reactor; hydrogenation reaction substrate methyl pyruvate (0.5mmol) and 2ml solvent join in this reactor; the hydrogenation substrate is transferred in this reactor; continue behind the hydrogen exchange 3 times to feed hydrogen, keep 60 kilograms of pressure in 60 ℃ of reactions cessation reaction after 6 hours.Filter with short silicagel column, will filter after gained filtrate concentrates, carry out content and optical purity is measured with GC, get S-methyl lactate yield 100% (in methyl pyruvate), enantiomeric excess is 99.0%ee.
Relevant comparative example 1
Press embodiment 1, the monodentate phosphinate part of use Reetz etc. is made the asymmetric hydrogenation of Rh catalyst α-dehydroamino acid ester, only can obtain 95.5%ee.
Relevant comparative example 2
Press embodiment 7, the monodentate phosphinate part of use Reetz etc. is made the asymmetric hydrogenation of the enamine of Rh catalyst, can only be at higher pressure, and 60atm reaction down, and only obtain 95.3%ee.
Claims (7)
1, a kind of chiral ligand metal complex to catalyze system, the system that complex compound that is formed by part and metal Rh, Ru, Ir, Pt or Pd metal or part and respective metal precursor are formed by 1～2 mol ratio; Wherein part has following structure and structural formula name:
Wherein, the R in the part
1, R
2Group is: the C of hydrogen, phenyl, substituted-phenyl, 1-naphthyl or 2-naphthyl
6-C
60The interior aromatic group that contains N, S, O, P; The C of methyl, ethyl, propyl group or butyl
1～C
40The interior fat group that contains N, S, O, P;
In the part
Group is:
Wherein, R=HR=CH3R=Ph
Wherein, R1=CH3 R2=HR1=CH3 R2=CH3R1=OCH3 R2=HR1=OCH3 R2=CH3
Wherein, R1=CH3 R2=H, R2=CH3 R1=H.R1=CH3 R2=CH3, R1=Ph R2=H.R1=OCH3 R2=H, R2=OCH3 R1=H.R1=OCH3 R2=CH3, R2=OCH3 R1=CH3, R1=t-Bu R2=1-Bu, R1=Si (
CH
3) 3 R2=H. R1=t-Bu R2=H, R2=1-Bu R1=H,
2, a kind of method for preparing part in the described catalyst system and catalyzing of claim 1 the steps include:
A) aldehyde in molar ratio: sweet mellow wine: the concentrated sulfuric acid is 1: 4.4: 2, join in the organic solvent that equates with above-mentioned cumulative volume, reaction is 10-80 hour under the stirring at room, the reactant mixture filtration is obtained solid and uses petroleum ether, the solids chloroform extracting of boiling, the solids that filtration obtains is through recrystallizing methanol;
B) solids that step 1 is obtained, sodium hydride and halogenated aliphatic hydrocarbon are to join in organic solvent at 1: 1: 1.1 in molar ratio, under the room temperature stirring reaction 0.5-3 hour, reactant mixture extracted with diethyl ether, saline solution washing, anhydrous sodium sulfate drying is removed solvent and is obtained solids;
C) under the nitrogen protection, will poly-2 solids that obtain of step drip triethylamine in 0-5 ℃, dropwise the back, add diphenol again under room temperature stirring reaction 1-3 hour, filter, remove solvent and obtain required part through the ether recrystallization stirring at room reaction 5-30 minute; Mol ratio in this step is a solids: diphenol: phosphorus trichloride: triethylamine=1: 1.2: 1: 2.2.
3, preparation method as claimed in claim 2 is characterized in that, aldehyde used among the step a is C
1-C
60Fatty aldehyde or C
6-C
30Aromatic aldehyde;
4, preparation method as claimed in claim 3 is characterized in that, used aldehyde is formaldehyde, acetaldehyde or benzaldehyde among the step a.
5, preparation method as claimed in claim 2 is characterized in that, used halogenated aliphatic hydrocarbon is that iodomethane, aromatic hydrocarbons replace halogenated methyl, aromatic hydrocarbons replaces halogenated methylene or aromatic hydrocarbons replaces the halo methine among the step b.
6, preparation method as claimed in claim 1 is characterized in that, used diphenol is 2 among the step c, 2 '-dinaphthalene diphenol, 3,2 of 3 ' replacement, 2 '-dinaphthalene diphenol, 2,2 of 2 '-'-biphenyl diphenol or replacement, 2 '-'-biphenyl diphenol.
7, the application of the described chiral monodentate phosphorus of above-mentioned each claim part asymmetric hydrogenation in C=C, C=O, C=N key.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03152667 CN1579627A (en) | 2003-08-05 | 2003-08-05 | Chiral ligand metal complex catalyst system, and its preparation method and use |
| PCT/CN2004/000777 WO2005011863A1 (en) | 2003-08-05 | 2004-07-09 | A chiral ligand metalcomplex catalyst system and its preparation and applications |
Applications Claiming Priority (1)
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| CN102532225A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Chiral phosphate ester ligand derived from methyl glucoside as well as preparation method and application thereof |
| CN106040299A (en) * | 2016-05-30 | 2016-10-26 | 北京理工大学 | Chiral diene rhodium metal catalyst and preparation method and application thereof |
| CN110963902A (en) * | 2019-12-05 | 2020-04-07 | 万华化学集团股份有限公司 | Method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation and catalyst used in method |
| CN111185241A (en) * | 2020-03-09 | 2020-05-22 | 邯郸学院 | Metal catalyst and preparation method and application thereof |
| CN111285774A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院大连化学物理研究所 | Asymmetric imine hydrogenation method based on chiral monodentate phosphine ligand derived from D-mannitol |
| CN111285773A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院大连化学物理研究所 | Method for preparing chiral amine based on glucose-derived monodentate phosphite ligand asymmetric hydrogenation |
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| CN114573473A (en) * | 2022-03-03 | 2022-06-03 | 浙江工业大学 | Preparation method of (R) -alpha-aryl alanine ester derivative |
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| CN1212254A (en) * | 1997-09-25 | 1999-03-31 | 中国科学院兰州化学物理研究所 | Method for preparing naproxen of methyl ester and S-(+) naproxen of methyl ester by using carbonylation |
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| GB0120167D0 (en) * | 2001-08-17 | 2001-10-10 | Chirotech Technology Ltd | Asymmetric hydrogenation |
| CN1166672C (en) * | 2001-12-07 | 2004-09-15 | 中国科学院上海有机化学研究所 | Metal complex of C2 uncymmetric chira biphosphine ligand, its synthesizing process and its application in unsymmetric catalytic hydrogenation of ketone |
| CN1166671C (en) * | 2001-12-07 | 2004-09-15 | 中国科学院上海有机化学研究所 | C2 unsymmetric chiral biphosphine ligand and its synthesizing method and application |
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2003
- 2003-08-05 CN CN 03152667 patent/CN1579627A/en active Pending
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