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CN1168889A - Chiral phosphine aminate-metal coordinate compound, the prepn. method thereof and the application in the asymmetrically catalytic hydrogenation - Google Patents

Chiral phosphine aminate-metal coordinate compound, the prepn. method thereof and the application in the asymmetrically catalytic hydrogenation Download PDF

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CN1168889A
CN1168889A CN 97112606 CN97112606A CN1168889A CN 1168889 A CN1168889 A CN 1168889A CN 97112606 CN97112606 CN 97112606 CN 97112606 A CN97112606 A CN 97112606A CN 1168889 A CN1168889 A CN 1168889A
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高景星
许翩翩
黄培强
万惠霖
蔡启瑞
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Xiamen University
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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
    • B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • 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)
    • 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
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0255—Ligands comprising the N2S2 or N2P2 donor atom set, e.g. diiminodithiolates or diiminodiphosphines with complete pi-conjugation between all donor centres
    • 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
    • B01J2531/821—Ruthenium

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Abstract

The present invention uses optical active (R) and (R, R), (S) or (S,S) diamine to synthesize diphosphine-diamine optical active chiral compounding substance which is used as chiral catalystto proceed asymmctric reduction of aromatic ketone, the reaction can proceed under 20-30 deg. C and 1 atm., th chemical yield of product optical active aromatic alcohol is 92%, and the optical yield is 91%. Furthermore, it can be oriented to produce levo-aromatic and dextro-aromatic alcohols, being an important intermediate to synthesize clural medicines of different arylamino alwhol structures.

Description

Chiral Amine phosphine metal complexes and preparation method thereof and in the application of asymmetric catalytic hydrogenation
The present invention relates to a kind of precursor structure and contain two nitrogen-atoms, two phosphine atoms and a central metal ion metal complexes.
The optical activity aromatic alcohol is the important intermediate of synthetic α-aromatic amine alcohols chiral drug.α-aromatic amine alcohol (n=1, R=H) and the ether that derives (n=2, R=aryl) be respectively the basic structure that chiral drugs such as (fluaxetine) is ordered in receptor, agonist class anti-asthmatic (as bronchodilator-salbutamol Salbutamol) and thymoleptic fluorine west.There is difference in various degree in the physiologically active of left-handed (the R-body) of these chiral drugs and dextrorotation (S-body) enantiomorph, but at present all with the formal city of racemize, and in fact the purity of racemic drugs have only 50%.Use problems such as the caused drug effect of this class medicine, metabolism and toxicity more and more to be paid close attention to.Therefore develop the aromatic amine alcohols medicine of single enantiomer, will give security for the validity and the security of drug use.
The aromatic alcohol of synthesis of optically active has several different methods at present, but not very good.E.J.Gorey had once reported method (Tetrahedron Lett., 30,520-523,1989 of carrying out the aromatic ketone asymmetric reduction with the chirality borane reagent; J.Org.Chem., 56,442,1991; Tetrahedron lett., 30,5207～5210; Tetrahedron lett., 31,601～604,1990).U.S. Pat 4918246, (1990) disclose similar method, but these class methods need be with stoichiometric chiral reduction agent.Vemishetti has reported method (the Synthetic Commun. with chiral catalyst asymmetric reduction aromatic ketone, 25,1093～1098,1995), but the percent enantiomeric excess of product (ee value) has only 29.5%～85.0%, and needs with 70 atmospheric hydrogen.Famous chiral diphosphine complex B LNAP-Ru (II) is though the asymmetric hydrogenation of the multiple aromatic ketone of energy catalysis, but the asymmetric hydrogenation to simple aromatic ketone such as methyl phenyl ketone still is difficult to realize (R.Noyori, " Asymmetric Catalysis in Organic Synthesis ", John Wiley α Sow, Inc., 1994).
Purpose of the present invention aims to provide the metal complexes that a class contains the chiral ligand of diamine-two phosphines.As chiral catalyst, under near room temperature and normal pressure, realize the asymmetric hydrogenation of aromatic ketone smoothly with this class title complex, its chemical yield and optical yield all reach 91%.
The general structure of Chiral Amine phosphine metal complexes provided by the invention is R wherein 1=H, CH 3, C 6H 5 -
R 2=H, CH 3, C 6H 5 -M=Ru, Rh, Pd, Cu, Ag, Cr, Mo; L=Cl, Br, CH 3COO -, do not have.The synthetic route of Chiral Amine phosphine metal complexes is as follows:
Figure A9711260600051
Its synthesis step is as follows:
Step 1: neighbour-diphenylphosphine phenyl aldehyde (compound 1) is in the presence of a kind of dewatering agent, and by R 1And R 2The optically active adjacent diamines of tool (compound 2) of definition a kind of fontanel for hydrocarbon solvent in, in 15～42 ℃ of following stirring reactions 40～55 hours, the product C of gained behind the solvent was filtered, removes under reduced pressure in especially 20～30 ℃ of reactions 45～50 hours down then 1～C 2Fontanel is for hydrocarbon and C 1～C 3Alcohol mixed solvent recrystallization obtains by R 1And R 2The compound 3 (mp.60～63 ℃) of definition.Said fontanel is C for hydrocarbon solvent 1～C 2Fontanel is for hydrocarbon, particularly methylene dichloride or chloroform; Dewatering agent refers to anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous or anhydrous calcium oxide; The optically active adjacent diamines of tool is (s)-adjacent diamines, (s, s)-adjacent diamines, (R)-adjacent diamines or (R, R)-adjacent diamines, R 1And R 2Be H, C 1～C 8Alkyl or aryl, particularly methyl, phenyl, 2-naphthyl or substituted aryl do not comprise R 1And R 2Be the diamines of hydrogen simultaneously.
Step 2: compound 3 and excessive sodium borohydride are in methyl alcohol or alcohol solvent, reacted 40～60 hours down in 56～78 ℃, add water and aqueous ammonium chloride solution, use methylene dichloride, imitative or the ethyl acetate extraction of hydrogen, extraction liquid washes with water, again through anhydrous magnesium sulfate drying, filter at last, after the removal of solvent under reduced pressure compound 4 (mp.59～62 ℃), the mol ratio that said excessive sodium borohydride refers to compound 3 and sodium borohydride is 1: 15～1: 20.
Step 3: compound 4 and a kind of transition metal complex are in a kind of solvent, reacted 12～20 hours down in 40～130 ℃, reaction solution gets compound 5 behind silica gel column chromatography, and said transition metal complex is Ru, Pd, Cu, Rh, Ag, Cr, the fontanelle compound of Mo, nitrile compound, boron fluoride or carbonyl compound; Said solvent is a methylene dichloride, chloroform, 1,2-ethylene dichloride, chlorobenzene, benzene, toluene or dimethylbenzene.
With title complex 5 is the asymmetric reduction that chiral catalyst is applied to aromatic ketone, and under 20～30 ℃, 1 normal atmosphere, optical activity aromatic alcohol chemical yield reaches 92%, optical yields 91%.Concrete grammar is as follows:
Figure A9711260600061
Under a kind of inert atmosphere, successively optical activity chirality title complex 5, solvent, aromatic ketone 6 and a certain amount of alkali lye are joined in the reaction flask aromatic ketone: catalyzer: the mol ratio of alkali is (100～200): 1: (1～5).Mixture 0～50 ℃ of following stirring reaction 5～96 hours, obtains the optical activity aromatic alcohol behind concentrating under reduced pressure, the silica gel column chromatography in the presence of a kind of reductive agent.Said inert atmosphere is nitrogen or helium; Solvent is C 2～C 4The mixing solutions of pure and mild methylene dichloride or toluene, particularly ethanol, Virahol or isopropylcarbinol; Aromatic ketone is n=1～2, and 1～2 hetero atom substituents is arranged on the phenyl ring, and x is a hydrogen, chlorine, bromine, amide group, ester class or carboxyl; Reductive agent is a hydrogen, and hydroborate maybe can produce the reagent system of active hydride, as Virahol-potassium isopropoxide, and Virahol-potassium hydroxide or isopropylcarbinol-isobutyl potassium alcoholate.
The possible mechanism of this compounds catalysis aromatic ketone asymmetric hydrogenation can Ru title complex be that example illustrates, the ruthenium catalyst system is in the presence of alkaline solution and reductive agent Virahol-potassium isopropoxide, the at first fracture of iso-Pro-attack ruthenium center and promotion Ru-Cl key, (as shown in Figure 1, A is an aromatic ketone), generate different third alkoxyl group-ruthenium intermediate, the reactive hydrogen on the isopropoxy is transferred to the ruthenium center and is generated active specy Ru-H then, and then the intramolecularly hydrogen transference takes place, generate phenylethyl alcohol.After reaction product is disengaged, isopropoxy again with the coordination of ruthenium active centre, regenerate isopropoxy ruthenium intermediate, circulation so repeatedly realizes the hydrogen transference hydrogenation.Compound 5 has the octahedra configuration of hexa-coordinate, the strong rigidity of molecule tool, and a plurality of phenyl ring plane of chiral ligand (compound 4) generates the three-dimensional microenvironment of chirality around the ruthenium atom of center, cause high ee value.
The present invention from optically active (R) or (R, R), (S) or (S, S) diamines sets out, and has synthesized two phosphines-diamine optical activity chirality part and title complex.And be the asymmetric reduction that chiral catalyst carries out aromatic ketone with these title complexs, can under mild conditions, (20～30 ℃, 1 normal atmosphere) carry out, optical activity aromatic alcohol chemical yield reaches 92%, and optical yields is up to 91%, and orientation control generates left-handed or dextrorotation aromatic alcohol on an equal basis easily.This catalyzer can be applied to contain the asymmetric catalytic hydrogenation reaction of C=C or C=N functional group substrate, and can be used for synthetic multiple important intermediate with chiral drug of arylamines alcohol class formation.
Fig. 1 is that chiral ruthenium complex asymmetry catalysis aromatic ketone hydrogen transference hydrogenant may the mechanism synoptic diagram.
The invention will be further described with embodiment below.
Embodiment 1:
Step 1: get 2.18g neighbour-diphenylphosphine phenyl aldehyde, 0.28g (S)-1,2-propylene diamine and 5.3g anhydrous sodium sulphate are in the 30ml methylene dichloride, 25 ℃ were stirred 48 hours down, filtered, and got 2.02g light yellow crystal 3 behind the pressure reducing and steaming solvent, yield 87%, mp.60～63 ℃.
Step 2: in ethanol, 78 ℃ of reactions 48 hours down add 10ml water and 10ml saturated ammonium chloride successively with 1.85g (S)-3 and 2.27g sodium borohydride.With dichloromethane extraction three times.Extraction liquid washes with water and anhydrous magnesium sulfate drying successively.Filter, obtain 1.41g faint yellow solid 4 after the removal of solvent under reduced pressure, yield 75%, mp.59～62 ℃.
Ultimate analysis C 41H 40N 2P 2: experimental value (calculated value), %:C 78.62 (79.12); H 6.50 (6.43); N 4.20 (4.50).IR(KBr)：3411m，3057m，1478m，1431vs，1374m，1156m，1089m，1024w，744vs，696vs，545m，497m，cm -1。 1H?NMR(CDCl 3)：C 6H 5 -，δ6.87～7.62(28H，m)；phCH 2 -，δ4.14(2H，m)，3.99(2H，m)；-NH-，δ2.85(2H，s)；
Figure A9711260600071
δ2.67(1H，s)；-CH 2-，2.63(2H，m)；-CH 3，1.07(3H，d，J H-H＝6.3Hz)ppm。 31p(CDCl 3)：δ-15.41，-15.51ppm。
Step 3: with 0.31g compound (S)-4 and 0.24g Ru (DMSO) 4Cl 2Reaction is 15 hours in the toluene that refluxes, reaction solution through silicagel column separate obtain 0.32g yellow crystals 5 (M=Ru, L=Cl), yield 81%, mp.226～228 ℃.
Ultimate analysis C 41H 40N 2P 2Cl 2Ru0.5C 6H 14: experimental value (calculated value), %:C 63.04 (63.11); H 5.46 (5.61); N 3.35 (3.34).IR(KBr)：3450m，3057m，2867m，1474s，1431vs，1027w，1089s，950s，744s，692vs，516vs?cm -1。 1H?NMR(CDCl 3)：C 6H 5 -，δ6.82～7.34(28H，m)；phCH 2 -，δ4.80(1H，t，J H-H＝11Hz)，4.75(1H，t，J H-H＝11Hz)，4.06(1H，d，J H-H＝12Hz)，3.70(1H，d，J H-H＝12Hz)； δ3.54(1H，m)；-NH-，δ4.62(1H，s)，3.95(1H，t，J H-H＝12Hz)；-CH 2-，δ3.28(1H，t)，3.01(1H，d)；-CH 3，0.91(3H，d，J H-H＝5.8Hz)ppm。31p(CDCl 3)：δ+45.41，+43.88ppm。
Step 4: under nitrogen atmosphere, 7.94mg compound (S)-5 is dissolved in 24ml Virahol and the 1ml toluene mixture liquid, adds the aqueous isopropanol of the potassium isopropoxide of 20mg methyl phenyl ketone and 0.3ml 0.1M.Ketone: catalyzer: the mol ratio of alkali is 100: 1: 3.Reactant is under 30 ℃, and stirring reaction 46 hours generates (S)-phenylethyl alcohol, and through gas chromatographic analysis (50 meters long for chirality capillary chromatographic column CP-Cyclodextrin-β-2,3,6-M-19), chemical yield is 92%.(S)-percent enantiomeric excess (e.e value) of phenylethyl alcohol is 91%.
Embodiment 2:
Step 1: in the step 1 of embodiment 1, use hydrogen instead and imitate the replacement methylene dichloride, reacted 42 hours down, get an oily matter after decompression desolventizes, from CH at 40 ℃ 2Cl 2/ EtOH recrystallization gets 1.41g product 3, yield 62%.
Step 2: in the step 2 of embodiment 1, use methyl alcohol instead and replace ethanol to make reaction solvent,, obtain 1.12g product 4, yield 60% 56 ℃ of following back flow reaction 60 hours.
Step 3: in the step 3 of embodiment 1, use benzene instead and replace toluene, refluxed 20 hours down at 80 ℃, obtain 0.25g yellow crystals 5 (M=Ru, L=Cl), yield 52%.
Step 4: in the step 4 of embodiment 1, replace toluene with the 1ml methylene dichloride, stirring reaction is after 52 hours, (S)-and the chemical yield and the ee value of phenylethyl alcohol be respectively 78% and 81%.
Embodiment 3: make compound 4 with embodiment 1 method, (0.311g is 0.5mmol) with palladium nitrile title complex Pd (CH 3CN) 2Cl 2(0.130g, 0.5mmol) the CH of backflow 2Cl 2(15ml) reaction generates orange solution and some precipitations, reaction solution is concentrated into about 10ml, in refrigerator overnight, after filtration, ether washes the back drying under reduced pressure, 0.32g yellow solid ((S)-PdCl 2(P 2N 2H 4Me)), yield 80.1%, mp.186～189 ℃.
Under helium-atmosphere, 7.94mg above-claimed cpd (S)-5 is dissolved in 24ml ethanol and the 1ml toluene mixing solutions, between adding 155mg-chlormezanone.All the other conditions were reacted 96 hours with embodiment 1, and the chemical yield and the optical yield that generate (S)-chlorophenethylol are respectively 96% and 88%.
Embodiment 4: make compound 4 with embodiment 1 method, get 0.309g compound 4 (0.5mmol) and title complex C then 7H 8Mo (CO) 4(0.15g, 0.5mmol) back flow reaction 16 hours in the 15ml tetrahydrofuran (THF), a dark red solution, through SiO 2Chromatographic column is separated, and uses CH 2Cl 2Be leacheate, the CH of collection 2Cl 2Solution gets the mauve crystal of 0.32g ((S)-P behind drying under reduced pressure 2N 2H 4MeMo (CO 4)), yield 77%, mp.143～147 ℃.
Step 4 with embodiment 1, replace methyl phenyl ketone with the 134mg Propiophenone, with above-claimed cpd (S)-5 is catalyzer, add 0.1M potassium isopropoxide 0.2ml (Propiophenone: catalyzer: the mol ratio of alkali is 100: 1: 2), after 24 hours, the chemical yield and the optical yield that generate (S)-phenylpropyl alcohol are respectively 85% and 76% at 30 ℃ of stirring reactions.
Embodiment 5: identical with the method for embodiment 1, only with (S)-1, the 2-propylene diamine changes (R)-1 into, and 2-propylene diamine, reaction conditions are all constant, and the chemical yield and the optical yield that generate (R)-phenylethyl alcohol at last are respectively 92% and 91%.
Embodiment 6: identical with the method for embodiment 1, with (S)-1, the 2-propylene diamine is used (R)-1, the 2-propylene diamine replaces, and generates compound (R)-5, replaces Propiophenone with a mono chloro benzene ketone again, generate (R)-chlorophenethylol, its chemical yield and optical yield are respectively 95% and 89%.

Claims (4)

1. Chiral Amine phosphine metal complexes is characterized in that its general structure is R wherein 1=H, CH 3, C 6H 5 -
R 2＝H，CH 3，C 6H 5 -；
M＝Ru，Rh，Pd，Cu，Ag，Cr，Mo；
L=Cl, Br, CH 3COO -, do not have.
2. the preparation method of Chiral Amine phosphine metal complexes is characterized in that synthesis step is as follows:
Step 1: neighbour-diphenylphosphine phenyl aldehyde (compound 1) is in the presence of a kind of dewatering agent, and by R 1And R 2The optically active adjacent diamines of tool (compound 2) of definition in a kind of halogenated hydrocarbon solvent, in 15～42 ℃ of following stirring reactions 40～55 hours, filter then, steam desolventize after recrystallization again, obtain by R 1And R 2The compound 3 (m.p.60～63 ℃) of definition, said dewatering agent is an anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous or anhydrous calcium oxide, the optically active adjacent diamines of tool is (s)-adjacent diamines, (s, s)-adjacent diamines, (R)-adjacent diamines or (R, R)-adjacent diamines, R 1And R 2Be H, C 1～C 8Alkyl or aryl;
Step 2: compound 3 and excessive sodium borohydride are in methyl alcohol or alcohol solvent, reacted 40～60 hours down in 56～78 ℃, add water and aqueous ammonium chloride solution, use methylene dichloride, imitative or the ethyl acetate extraction of hydrogen, extraction liquid washes with water, again through anhydrous magnesium sulfate drying, filter at last, after the removal of solvent under reduced pressure compound 4 (mp.59～62 ℃), compound 3 is 1: 15～1: 20 with the mol ratio of sodium borohydride;
Step 3: compound 4 and a kind of transition metal complex reacted 12～20 hours down in 40～130 ℃ in a kind of solvent, and reaction solution gets Chiral Amine phosphine metal complexes (compound 5) behind silica gel column chromatography, and transition metal complex is Ru, Pd, Cu, Rh, Ag, Cr, the fontanelle compound of Mo, nitrile compound, boron fluoride or carbonyl compound, solvent are methylene dichloride, chloroform, 1, the 2-ethylene dichloride, chlorobenzene, benzene, toluene or dimethylbenzene.
3. the preparation method of Chiral Amine phosphine metal complexes as claimed in claim 2 is characterized in that the compound in the step 11 and the temperature of reaction of compound 2 are 20～30 ℃, and in 45～50 hours reaction times, said fontanel is methylene dichloride or chloroform for hydrocarbon solvent, R 1And R 2Be methyl, phenyl, 2-naphthyl or substituted aryl.
4. Chiral Amine phosphine metal complexes is in the application of asymmetric catalytic hydrogenation, it is characterized in that with Chiral Amine phosphine metal complexes be chiral catalyst in the asymmetric reduction reaction of aromatic ketone, its method is: under hydrogen or nitrogen atmosphere, successively with compound 5 solvents, aromatic ketone and a certain amount of alkali lye add in the reaction flask, aromatic ketone: catalyzer: the mol ratio of alkali is (100～200): 1: (1～5), mixture is in the presence of a kind of reductive agent, 0～50 ℃ of following stirring reaction 5～96 hours, concentrating under reduced pressure, obtain the optical activity aromatic alcohol behind the silica gel column chromatography, said solvent is C 2～C 4The mixing solutions of pure and mild methylene dichloride or toluene, reductive agent are hydrogen, hydroborate or Virahol-potassium isopropoxide, Virahol-potassium hydroxide, isopropylcarbinol-isobutyl potassium alcoholate.
CN97112606A 1997-06-02 1997-06-02 Chiral phosphine aminate-metal coordinate compound, the prepn. method thereof and the application in the asymmetrically catalytic hydrogenation Expired - Fee Related CN1047597C (en)

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WO2002040155A1 (en) * 2000-11-17 2002-05-23 Firmenich S.A. Process for hydrogenation of carbonyl and iminocarbonyl compounds using ruthenium catalysts comprising tetradentate diimino-diphosphine ligands
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WO2002040155A1 (en) * 2000-11-17 2002-05-23 Firmenich S.A. Process for hydrogenation of carbonyl and iminocarbonyl compounds using ruthenium catalysts comprising tetradentate diimino-diphosphine ligands
CN101142155B (en) * 2005-04-05 2011-06-01 弗门尼舍有限公司 Hydrogenation of esters with ru/tetradentate ligands complexes
CN102245562B (en) * 2008-12-18 2014-08-13 弗·哈夫曼-拉罗切有限公司 Process for synthesis of amino-methyl tetraline derivatives
CN102245562A (en) * 2008-12-18 2011-11-16 弗·哈夫曼-拉罗切有限公司 Process for synthesis of amino-methyl tetraline derivatives
CN102553646A (en) * 2011-12-20 2012-07-11 厦门大学 Chiral diamine diphosphine metal compound catalysts as well as preparation method and application thereof
CN102553646B (en) * 2011-12-20 2013-10-23 厦门大学 Chiral diamine diphosphine metal compound catalysts as well as preparation method and application thereof
CN103570771A (en) * 2013-11-06 2014-02-12 江苏长青农化股份有限公司 Method for synthesizing 1-ferrocenylethanol
CN103962152A (en) * 2014-04-28 2014-08-06 上海师范大学 Ru-Pd bi-metal loading chiral catalyst and preparation technology thereof
CN109735942A (en) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 High mode and low mode activated polyester industrial yarns and preparation method thereof
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CN113797977A (en) * 2020-06-12 2021-12-17 沈阳中化农药化工研发有限公司 Ruthenium catalyst and application thereof
CN113797977B (en) * 2020-06-12 2022-11-29 沈阳中化农药化工研发有限公司 Ruthenium catalyst and application thereof
CN114289073A (en) * 2021-10-21 2022-04-08 长春工业大学 Method for producing hydrogen by methanol and water reforming under homogeneous catalysis of Schiff base metal complex
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