CN100389877C - Supported catalyst for preparing chiral secondary alcohol under normal pressure and method for preparing the same - Google Patents
Supported catalyst for preparing chiral secondary alcohol under normal pressure and method for preparing the same Download PDFInfo
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Abstract
The present invention relates to a supported catalyst which can be used for preparing chiral disubstituted carbinol by the asymmetric catalysis hydrogenization of prochiral ketone under the condition of normal pressure, which belongs to the technical field of chirality. The present invention uses polyethyleneglycol macromolecules, etc. as carriers, MeO-Niphep, etc. as chiral phosphor ligands and ruthenium as transitional metal to prepare the macromolecule supported chiral catalyst. The catalyst can realize the reaction of chiral disubstituted carbinol preparation by the asymmetric catalysis hydrogenization of prochiral ketone under common temperature conditions (room temperature of 80DEG C) at normal pressure. The present invention avoids the use of high-pressure autoclaves and other high-pressure reaction devices, and the catalyst can be conveniently recovered for reuse. The present invention has the characteristics of simple and safe operation, quick reaction, high yield, good stereoselectivity, low cost, friendly environment, etc. and has practical industrial application value.
Description
Technical field
The invention belongs to the chiral technology field, be specifically related to a kind of supported catalyst that is used for preparing chiral secondary alcohol under normal pressure and preparation method thereof.
Background technology
Chiral, secondary alcohols is the important chipal compounds of a class, a lot of natural organic-compounds and have the structure that all contains chiral, secondary alcohols in the compound of physiologically active.As in the asymmetric syntheses of important antidepression class medicine Prozac of a class and analog thereof all with chiral, secondary alcohols as key intermediate (WO0007976, US6025517, EP457559).
In the method that comprises multiple acquisition chiral, secondary alcohols such as asymmetric catalytic hydrogenation, asymmetric hydrogen migration, asymmetric hydroboration, Sharpless bishydroxy, enzymic catalytic reaction, the asymmetric catalytic hydrogenation prochiral ketone is considered to now effective method.The chirality Binap-Ru catalyst hydrogenation prochiral ketone of being started as the Noyori of Japan professor can high yield, highly-solid selectively ground acquisition chiral, secondary alcohols (Noryori, R; J.Am.Chem.Soc.1987,109,5856; EP0470756).But, the synthetic difficulty of employed chiral phosphine ligand, the costliness that noble ruthenium is also suitable, and the homogeneous reaction post processing is loaded down with trivial details, expensive and virose catalyst can not reclaim repeated use, and precious metal ion has influenced its application in medicine is synthetic again after entering product.These have all limited above-mentioned catalyst in industrial being extensive use of.
Though working load catalyst asymmetric catalytic hydrogenation prochiral ketone has had certain research (Baysion.D.J.J.Org.Chem, 1998,63,3137; US5736480), but because the influence of macromolecule carrier, (20～150atm) and higher temperature, the reaction time is prolonged greatly, and catalyst amount also needs greatly to improve, and the optical purity of product is desirable not to the utmost to need higher Hydrogen Vapor Pressure in the reaction.These shortcomings have been covered the macromolecule load catalyst characteristics of recycling easily, and especially huge energy consumption and not high optical purity are unfavorable factors for its commercial Application.
Summary of the invention
The objective of the invention is to propose a kind ofly to be swift in response, easy and safe to operate, productive rate good, optical purity of products is high, preparation chiral, secondary alcohols with low cost and eco-friendly is used supported catalyst and preparation method thereof.
The supported catalyst that the present invention proposes is by load part and ruthenium complex (COD) Ru (CH
2-C (CH
3)=CH
2)
2In acetone, react acquisition with the hydrogen bromide methanol solution.Wherein, load part: (COD) Ru (CH
2-C (CH
3)=CH
2)
2=(1-2): 1, (COD) Ru (CH
2-C (CH
3)=CH
2)
2: HBr=1: (2-3); The load part here is by macromolecule carrier and chirality diphosphine ligand and alkali prepared in reaction acquisition in organic solvent, and wherein, chirality diphosphine ligand: macromolecule carrier=1: (1-3), chirality diphosphine ligand: alkali=1: (1-4), aforementioned proportion is mol ratio.
The preparation method of above-mentioned supported catalyst is as follows:
1, the preparation of load part: in organic solvent, react reaction temperature by macromolecule carrier and chirality diphosphine ligand and alkali: 40-80 ℃, reaction time 10-30 hour.Wherein, the input amount of material component is calculated in molar ratio as: chirality diphosphine ligand: macromolecule carrier=1: (1-3), and chirality diphosphine ligand: alkali=1: (1-4);
2, the preparation of supported catalyst:
By load part and ruthenium complex (COD) Ru (CH
2-C (CH
3)=CH
2)
2In acetone, react reaction temperature with the hydrogen bromide methanol solution: 10-30 ℃, reaction time: 20-50 minute; Wherein, the material component input amount is calculated in molar ratio as: the load part: (COD) Ru (CH
2-C (CH
3)=CH
2)
2=(1-2): 1, (COD) Ru (CH
2-C (CH
3)=CH
2)
2: HBr=1: (2-3).
Among the present invention, described alkali can be selected a kind of of cesium carbonate, sodium carbonate, potash, potassium phosphate, potassium acetate, NaOH, potassium hydroxide or triethylamine for use, and is best with the cesium carbonate effect.
Among the present invention, described organic solvent can be selected DMF (trimethyl formamide), DMA (pivaloyl amine) or acetone etc. for use.
Among the present invention, macromolecule carrier in the described load part can be selected polyethylene glycols (DEG) macromolecular material for use, especially can select for use molecular weight to be respectively 2000,4000 and 5000 poly glycol monomethyl ether, is designated as MeO-PEG-2000 respectively, MeO-PEG-4000, MeO-PEG-5000.
The present invention also proposes to use above-mentioned supported catalyst under normal pressure prochiral ketone to be carried out the method that asymmetric catalytic hydrogenation prepares chiral, secondary alcohols, and concrete steps are as follows:
Described supported catalyst, prochiral ketone are mixed with organic solvent, under condition of normal pressure, carry out hydrogenation; Each amounts of components is counted in molar ratio, supported catalyst: prochiral ketone=1: (50～200), prochiral ketone: solvent=1: (2～20), reaction temperature: room temperature～80 ℃, 1～70 hour reaction time.
In the above-mentioned preparation chiral, secondary alcohols method, used organic solvent has organic solvents commonly used such as methyl alcohol, ethanol, carrene, chloroform, benzene, toluene, ethyl acetate or oxolane.Can select only solvent according to the concrete condition of producing.Preferred 50～60 ℃ of reaction temperature, the reaction time is as the criterion to react completely, preferred 1～5 hour.
Use this method not only can avoid using complicated high-pressure hydrogenation device, and be swift in response, productive rate is good, the optical purity height of product.Table 1 has provided the result of some typical substrate catalytic hydrogenations.
Some prochiral ketone of table 1 supported catalyst 4 asymmetric catalytic hydrogenations
The result of some typical substrate catalytic hydrogenations
Annotate: catalyst amount is 1%, and reaction temperature is 50 ℃
Even being catalyst, above-mentioned preparation method's characteristics under loading condition, still show high catalytic activity.Need exacting terms such as high pressure-temperature to compare with general supported catalyst, this supported catalyst can be realized the asymmetric catalytic hydrogenation to prochiral ketone under normal pressure and general heating.Compare with the precursor catalyst of not load, supported catalyst also shows higher catalytic activity.Under same reaction conditions, MeO-Biphep-RuBr
2(the not precursor catalyst of load) catalytic hydrogenation ethyl benzoylacetate 3 hours only has 23% conversion ratio; And supported catalyst catalytic hydrogenation ethyl benzoylacetate of the present invention 3 hours just can get the isolated yield (100% conversion ratio) more than 98%.Even like this high reactivity, supported catalyst still shows surprising stereoselectivity, the optical purity of a lot of catalytic hydrogenation products can reach 99% or more than.Reason wherein is to have selected macromolecule carrier for use, especially uses the polyethylene glycols macromolecule carrier, and this is a class soluble high-molecular.Supported catalyst dissolves in the reaction system, has also just reduced the stereoselective influence of macromolecular scaffold to chiral ligand to greatest extent.Simultaneously because the existence of macromolecule carrier, stoped the formation of active relatively poor ruthenium complex dimer, thereby improved the activity of supported catalyst.In addition, the polyethylene glycol family macromolecule has special solution behavior, also may be a reason that improves the supported catalyst reactivity.
Another one characteristics of the present invention are exactly that catalyst can recycling, and the post processing of reaction is also very convenient.The supported catalyst that this method is used is solvable in the used solvent of reaction.After reaction was finished, cooling adds ether down can be settled out the supported catalyst solid.Can also comprise t-butyl methyl ether, isopropyl ether and cold ethanol as the poor solvent of precipitating reagent.The addition of ether is that 1 gram supported catalyst needs 80～100 milliliters of ether.Supported catalyst can be separated it by the simple filtering washing with product, and can directly apply to down in the secondary response.Supported catalyst can be reused and reach more than 5 times, and the optical purity of product is constant substantially.To can obtain the product chiral, secondary alcohols after the solvent recovery in the filtrate, the ruthenium content in the ICP detection demonstration product is less than 10ppm.Also can be by decompression distillation or the further purified product of column chromatography.
The present invention is applicable to the asymmetric hydrogenation reduction of ketone carbonyl on beta-ketoester and the beta-keto acyl amine.
The present invention uses polyethylene glycol family macromolecule cheap and easy to get carrier as chiral ligand, synthetic loaded chiral catalyst has high activity, the characteristics of highly-solid selectively, realized that the asymmetric catalytic hydrogenation prochiral ketone prepares chiral, secondary alcohols under normal pressure, advantages such as it is rapid to respond, easy and safe to operate.And the post processing of reaction convenience very, supported catalyst can be reused, and has avoided poisonous precious metal ion to enter product.The chiral, secondary alcohols that this method obtains can be used for the preparation of some chiral drugs.
Description of drawings
Fig. 1 is supported catalyst synthetic route diagram.Wherein, condition is BBr in the step (a)
3, CH
2Cl
2, condition is in the step (b): MeO-PEG-OMs (Mw=2000), Cs
2CO
3, condition is in the step (c): (COD) Ru (CH
2-C (CH
3)=CH
2)
2, HBr/MeOH.
The specific embodiment
The invention is further illustrated by the following examples.
The preparation of supported catalyst:
Chirality methoxyl biphenyl biphosphine ligand MeO-Biphep (1) removes methyl on the methoxyl group with the Boron tribromide of triplication, temperature is controlled to be-78 ℃ during the reaction beginning, slowly rise to room temperature after about 1 hour, continue reaction 12 hours, so can obtain the chiral hydroxyl group biphenyl biphosphine ligand HO-Biphep (2) of 90% above productive rate.From commercially available methoxy poly (ethylene glycol) 2000 (MeO-PEG-2000),, generate methoxy poly (ethylene glycol) methanesulfonates (MeO-PEG-OMs) quantitatively then by reacting with mesyl chloride.MeO-PEG-OMs and HO-Biphep (2) are at the N of cesium carbonate, react in the solution of dinethylformamide (DMF) (or N, N-dimethylacetylamide (DMA), acetone etc.), productive rate with 90% generates the biphenyl biphosphine ligand (MeO-PEG-O-Biphep, 3) of methoxy poly (ethylene glycol) load.Wherein cesium carbonate also can use replacements such as sodium carbonate, potash, potassium phosphate, potassium acetate, NaOH, potassium hydroxide, triethylamine, but best with the effect that cesium carbonate was obtained.This load part and suitable ruthenium complex reaction, that the present invention uses is (COD) Ru (CH
2-C (CH
3)=CH
2)
2, getting final product the chiral catalyst that original position generates macromolecule loading, its synthetic route is seen shown in Figure 1.
Add (R)-MeO-Biphep (1) 11.7g (20mmol) and 300mL carrene in the 1000mL three-necked bottle.After being cooled to-78 ℃, find time to irritate nitrogen three times.Stirring and nitrogen protection drip the solution of 30g Boron tribromide in the 100mL carrene down, slowly are warming up to room temperature after dripping off, and stir and spend the night.Slowly add 200mL water after being cooled to 0 ℃, tell organic layer, and repeatedly wash organic facies with saturated sodium bicarbonate, use anhydrous sodium sulfate drying after the saturated common salt water washing, after the removal of solvent under reduced pressure, promptly obtain compound H O-Biphep (2), productive rate 90～95% is no longer purified and is directly used in the next step.
Add 26gMeO-PEG-OMs (12.4mmol) in the 500mL three-necked bottle under the nitrogen protection successively, 3.4gHO-Biphep (2) (6.2mmol), 8.0g cesium carbonate (24.4mmol) and 200mLDMF.Mixture (40～80 ℃) under heating condition reacted 10～36 hours, and GC follows the tracks of reaction, finishes until HO-Biphep (2) fundamental reaction.Most of DMF is removed in decompression, removes by filter inoganic solids, after filtrate is cooled to 0 ℃, add the 2000mL ether and stir 0.5h, solid collected by filtration is also used isopropyl alcohol and the ether washing, and obtaining compound (3) productive rate is 90%, and chiral ligand content is not less than 0.22mmol/g.
Add 26gMeO-PEG-OMs (12.4mmol) in the 500mL three-necked bottle under the nitrogen protection successively, 3.4gHO-Biphep (2) (6.2mmol), 3.6g potash (26.0mmol) and 200mLDMA.Mixture (40～80 ℃) under heating condition reacted 10～36 hours, and GC follows the tracks of reaction, finishes until HO-Biphep (2) fundamental reaction.Most of DMA is removed in decompression, removes by filter inoganic solids, after filtrate is cooled to 0 ℃, add the 2000mL ether and stir 0.5h, solid collected by filtration is also used isopropyl alcohol and the ether washing, and obtaining compound (3) productive rate is 90%, and chiral ligand content is not less than 0.20mmol/g.
Add 1.2g compound (3) in the 100mL three-necked bottle (0.264mmol) and 82mg (COD) Ru (CH
2-CH (CH
3)=CH
2)
2(0.257mmol), add the hydrobromic acid methanol solution of 20mL acetone and 3mL0.18M successively under nitrogen protection, react removal of solvent under reduced pressure after 0.5 hour under the room temperature, again through vacuum drying, promptly original position generates the catalyst (4) of load.
Embodiment 5
26.4mmol ethyl benzoylacetate is dissolved in (100mL) in the absolute ethyl alcohol, and this solution is joined in the loaded chiral catalyst (2%) of above-mentioned in-situ preparing, (50～70 ℃) carry out the normal pressure hydrogenation reaction under heating condition, GC follows the tracks of reaction, finish until the reaction of raw material ketone ester, the reaction time needs about 2 hours usually.Most of solvent is removed in decompression, and cooling adds 100～200mL ether down, filters the solid of collecting and can be used for hydrogenation next time.Filtrate is generally colourless transparent solution, is product behind the vacuum distillation recovered solvent, and productive rate is 98%; E.e.% is 92%.
Embodiment 6
26.4mmol ethyl benzoylacetate is dissolved in (50mL) in the absolute ethyl alcohol, and this solution is joined in the loaded chiral catalyst (1%) of above-mentioned in-situ preparing, (50～70 ℃) carry out the normal pressure hydrogenation reaction under heating condition, GC follows the tracks of reaction, finish until the reaction of raw material ketone ester, the reaction time needs about 3 hours usually.Most of solvent is removed in decompression, and cooling adds 100～200mL ether down, filters the solid of collecting and can be used for hydrogenation next time.Filtrate is generally colourless transparent solution, is product behind the vacuum distillation recovered solvent, and productive rate is 99%; E.e.% is 98%.
Embodiment 7
26.4mmol ethyl benzoylacetate is dissolved in (100mL) in the absolute ethyl alcohol, and this solution is joined in the loaded chiral catalyst (0.5%) of above-mentioned in-situ preparing, (50～70 ℃) carry out the normal pressure hydrogenation reaction under heating condition, GC follows the tracks of reaction, finish until the reaction of raw material ketone ester, the reaction time needs 4 hours usually.Most of solvent is removed in decompression, and cooling adds 100～200mL ether down, filters the solid of collecting and can be used for hydrogenation next time.Filtrate is generally colourless transparent solution, is product behind the vacuum distillation recovered solvent, and productive rate is 98%; E.e.% is 96%.
Embodiment 8
26.4mmol ethyl acetoacetate is dissolved in (100mL) in the absolute ethyl alcohol, and this solution is joined in the loaded chiral catalyst (2%) of above-mentioned in-situ preparing, (50～70 ℃) carry out the normal pressure hydrogenation reaction under heating condition, GC follows the tracks of reaction, finish until the reaction of raw material ketone ester, the reaction time needs 2 hours usually.Most of solvent is removed in decompression, and cooling adds the 100mL ether down, filters the solid of collecting and can be used for hydrogenation next time.Filtrate is generally colourless transparent solution, is product behind the vacuum distillation recovered solvent, and productive rate is 100%; E.e.% is 98%.
Embodiment 9
26.4mmol Propionylacetic acid ethyl ester is dissolved in (100mL) in the absolute ethyl alcohol, and this solution is joined in the loaded chiral catalyst (2%) of above-mentioned in-situ preparing, (50～70 ℃) carry out the normal pressure hydrogenation reaction under heating condition, GC follows the tracks of reaction, finish until the reaction of raw material ketone ester, the reaction time needs 3 hours usually.Most of solvent is removed in decompression, and cooling adds the 150mL ether down, filters the solid of collecting and can be used for hydrogenation next time.Filtrate is generally colourless transparent solution, is product behind the vacuum distillation recovered solvent, and productive rate is 97%; E.e.% is 99%.
For other ketone ester that the present invention mentions, by similar reaction condition, the product purity that obtains is greater than＞95%, and optical purity is 90～99%, productive rate 95-100%.Product can further be purified by decompression distillation or column chromatography, to meet the synthetic requirement of extension product.
Claims (5)
1. one kind prepares the supported catalyst that chiral, secondary alcohols is used, and it is characterized in that by load part and ruthenium complex (COD) Ru (CH
2-C (CH
3)=CH
2)
2In acetone, react acquisition with the hydrogen bromide methanol solution; Wherein, load part: (COD) Ru (CH
2-C (CH
3)=CH
2)
2=(1-2): 1, (COD) Ru (CH
2-C (CH
3)=CH
2)
2: HBr=1: (2-3); The load part here is by macromolecule carrier and chirality diphosphine ligand and alkali prepared in reaction acquisition in organic solvent, and wherein, chirality diphosphine ligand: macromolecule carrier=1: (1-3), chirality diphosphine ligand: alkali=1: (1-4), aforementioned proportion is mol ratio;
Here, described chirality diphosphine ligand is a chirality methoxyl biphenyl biphosphine ligand, and described macromolecule carrier is that relative molecular weight is 2000,4000 or 6000 poly glycol monomethyl ether.
2. the preparation method of a supported catalyst as claimed in claim 1 is characterized in that step is as follows:
(1) preparation of load part: in organic solvent, react reaction temperature by macromolecule carrier and chirality diphosphine ligand and alkali: 40-80 ℃, reaction time 10-30 hour; Wherein, the input amount of material component is calculated in molar ratio as: chirality diphosphine ligand: macromolecule carrier=1: (1-3), and chirality diphosphine ligand: alkali=1: (1-4);
(2) preparation of supported catalyst:
By load part and ruthenium complex (COD) Ru (CH
2-C (CH
3)=CH
2)
2In acetone, react reaction temperature with the hydrogen bromide methanol solution: 10-30 ℃, reaction time: 20-50 minute; Wherein, the material component input amount is calculated in molar ratio as: the load part: (COD) Ru (CH
2-C (CH
3)=CH
2)
2=(1-2): 1, (COD) Ru (CH
2-C (CH
3)=CH
2)
2: HBr=1: (2-3);
Here, described chirality diphosphine ligand is a chirality methoxyl biphenyl biphosphine ligand, and described macromolecule carrier is that relative molecular weight is 2000,4000 or 6000 poly glycol monomethyl ether.
One kind according to claim 1 supported catalyst asymmetric catalytic hydrogenation prochiral ketone under normal pressure prepare the method for chiral, secondary alcohols, it is characterized in that described supported catalyst, prochiral ketone are mixed with organic solvent, under condition of normal pressure, carry out hydrogenation; Each amounts of components is counted in molar ratio, supported catalyst: prochiral ketone=1: (50～200), prochiral ketone: solvent=1: (2～20), reaction temperature: room temperature～80 ℃, 1～70 hour reaction time.
4. method according to claim 3 is characterized in that described organic solvent is methyl alcohol, ethanol, carrene, chloroform, benzene, toluene, ethyl acetate or oxolane.
5. method according to claim 3 is characterized in that reaction temperature: 50～60 ℃, and 1～5 hour reaction time.
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| CN101279986B (en) * | 2007-04-05 | 2011-10-26 | 中国科学院大连化学物理研究所 | Synthetic method of axis-unsymmetric chiral diphosphine ligand |
| CN105218371A (en) * | 2015-09-24 | 2016-01-06 | 上海交通大学 | The preparation method of optically pure 3-hydroxyl-4-(2,4,5-trifluorophenyl) ethyl butyrate |
| CN109046465B (en) * | 2018-07-25 | 2021-03-26 | 华东师范大学 | Preparation and application of mesoporous silicon material immobilized chiral gold catalyst |
| CN110124732A (en) * | 2019-04-13 | 2019-08-16 | 复旦大学 | Polymer catalyst and preparation method thereof for metal catalyzed coupling reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103245A (en) * | 1984-04-19 | 1986-12-24 | 霍夫曼·拉罗奇有限公司 | The preparation of chirality rhodium-diphosphonic complex and the application in asymmetric hydrogenation thereof |
| US6350910B1 (en) * | 1999-06-17 | 2002-02-26 | Firmenich Sa | Stereospecific isomerisation of allylamines with the aid of immobilized phosphorated chiral ligands |
| CN1356334A (en) * | 2001-12-07 | 2002-07-03 | 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 |
| US20040220049A1 (en) * | 2000-11-03 | 2004-11-04 | Hems William Patrick | Catalyst |
-
2006
- 2006-03-30 CN CNB2006100252794A patent/CN100389877C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103245A (en) * | 1984-04-19 | 1986-12-24 | 霍夫曼·拉罗奇有限公司 | The preparation of chirality rhodium-diphosphonic complex and the application in asymmetric hydrogenation thereof |
| US6350910B1 (en) * | 1999-06-17 | 2002-02-26 | Firmenich Sa | Stereospecific isomerisation of allylamines with the aid of immobilized phosphorated chiral ligands |
| US20040220049A1 (en) * | 2000-11-03 | 2004-11-04 | Hems William Patrick | Catalyst |
| CN1356334A (en) * | 2001-12-07 | 2002-07-03 | 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 |
Non-Patent Citations (14)
| Title |
|---|
| 2,2'-甲氧基-6,6'-双(二苯基膦)联苯及其Ru(Ⅱ)配合物的合成和应用. 方春梅等.石油化工，第34卷. 2005 |
| 2,2'-甲氧基-6,6'-双(二苯基膦)联苯及其Ru(Ⅱ)配合物的合成和应用. 方春梅等.石油化工，第34卷. 2005 * |
| Asymmetric transfer hydrogenation of ketones witha polymer-supported chiral diamine. Xiaoguang Li et al.Tetrahedron Leeters,Vol.45 . 2004 |
| Asymmetric transfer hydrogenation of ketones witha polymer-supported chiral diamine. Xiaoguang Li et al.Tetrahedron Leeters,Vol.45 . 2004 * |
| Dendritic BIPHEP: Synthesis and application inasymmetric hydrogenation of β-ketoesters. Guo-Jun Deng et al.Journal of Molecular Catalysisi A: Chemical,Vol.244 . 2005 |
| Dendritic BIPHEP: Synthesis and application inasymmetric hydrogenation of β-ketoesters. Guo-Jun Deng et al.Journal of Molecular Catalysisi A: Chemical,Vol.244 . 2005 * |
| Novel, general synthesis of the chiralcatalysts diphosphine-ruthenium(Ⅱ) diallyl complexes and anew practical in situ preparation of chiral ruthenium(Ⅱ)catalysts. J.P. Genet et al.Tetrahedron: Asymmetry,Vol.5 No.4. 1994 |
| Novel, general synthesis of the chiralcatalysts diphosphine-ruthenium(Ⅱ) diallyl complexes and anew practical in situ preparation of chiral ruthenium(Ⅱ)catalysts. J.P. Genet et al.Tetrahedron: Asymmetry,Vol.5 No.4. 1994 * |
| Preparation and use of Meo-PEG-supported chiraldiphosphine ligands: soluble polymer-supported catalylstsforasymmetric hydrogenation. Qing-Hua Fan et al.Tetrahadron: Asymmetry,Vol.12 . 2001 |
| Preparation and use of Meo-PEG-supported chiraldiphosphine ligands: soluble polymer-supported catalylstsforasymmetric hydrogenation. Qing-Hua Fan et al.Tetrahadron: Asymmetry,Vol.12 . 2001 * |
| Preparation of polymer-supported Ru-TsDPEN catalystsand use for enantioselective synthesisi of (S)-fluoxetine. Yangzhou Li et al.Org. Biomol. Chem.,Vol.3 . 2005 |
| Preparation of polymer-supported Ru-TsDPEN catalystsand use for enantioselective synthesisi of (S)-fluoxetine. Yangzhou Li et al.Org. Biomol. Chem.,Vol.3 . 2005 * |
| Use of polymer-supported dialdylphosphinobiphenyl ligandsfor palladium-catalyzed amination and suzuki reactions. Cynthia a. Prrish et al.J. Org. Chem.,Vol.66 No.11. 2001 |
| Use of polymer-supported dialdylphosphinobiphenyl ligandsfor palladium-catalyzed amination and suzuki reactions. Cynthia a. Prrish et al.J. Org. Chem.,Vol.66 No.11. 2001 * |
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