CN102311299A - Method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction - Google Patents
Method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction Download PDFInfo
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- CN102311299A CN102311299A CN2010102171923A CN201010217192A CN102311299A CN 102311299 A CN102311299 A CN 102311299A CN 2010102171923 A CN2010102171923 A CN 2010102171923A CN 201010217192 A CN201010217192 A CN 201010217192A CN 102311299 A CN102311299 A CN 102311299A
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Abstract
The invention discloses a method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction, which is characterized in that phenyl ruthenium dichloride and chiral bridged biphosphine (Rax)-BuP and chiral diamine (R, R)-DPEN take reaction to prepare catalyst precursors, prochiral ketones and hydrogen gas are used as reactants, potassium tert-butoxide is used as auxiliary agents, and the chiral secondary alcohol is synthesized in one step through the asymmetric hydrogenation reaction in low-carbon alcohol solvents. The maximum reactant conversion rate can reach 99 wt percent, and the highest product corresponding selectivity can reach 92 percent.
Description
Technical field
The present invention relates to a kind of method of asymmetric hydrogenation synthesis of chiral secondary alcohol.
Background technology
Chiral, secondary alcohols is the important intermediate of synthesis of optically active medicine, and the catalysis asymmetry hydrogenation reaction of prochiral ketone is one of most effectual way that obtains chiral, secondary alcohols.In the asymmetric hydrogenation method of synthesis of chiral secondary alcohol, the key that obtains catalytic activity and enantioselectivity is a chiral ligand.Patent (EP-A-071826) openly has C
2Isomery dinaphthalene type biphosphine ligand (BINAP is changeed in the resistance of symmetry axis; Tol-BINAP, Xylyl-BINAP, H8-BINAP); With chiral diamine DPEN or DAIPEN; Catalyst precursor with the ruthenium preparation in the asymmetric hydrogenation of prochiral ketone, provides the product chiral alcohol of higher yields and enantioselectivity; Nineteen ninety-five, report such as the Noyori Ru-BINAP ternary system that verivate-chiral diamine-KOH forms, in the asymmetric hydrogenation of the prochiral ketone that does not contain other functional group, can be with the reactant Quantitative yield; The enantioselectivity of product is higher, (T.Ohkuma, H.Ooka; T.Ikariya, R.Noyori, J.Am.Chem.Soc.; 1995,117,2675).2009, Zhang etc. reported suc as formula the biphosphine ligand of biphenyl type shown in I C
3 *-Tunephos/ diamines-Ru (II) catalyst precursor shows excellent activity and enantioselectivity (W.Li, X.Sun, L.Zhou, G. Hou, S.Yu, X.Zhang, J.Org.Chem.2009,74,1397.) in the asymmetric hydrogenation of prochiral ketone.
Formula I
C3
*-Tunephos
Has C
2Isomery dinaphthalene type biphosphine ligand is changeed in the resistance of symmetry axis; Biphenyl type biphosphine ligand and dipyridyl type biphosphine ligand contain 3 on phosphorus atom; During 5-dimethyl benzene substituting group; Ruthenium catalyged precursor with the bigger chiral diamine of steric hindrance is formed in the asymmetric hydrogenation of prochiral ketone, shows relative advantages of high catalytic activity and enantioselectivity.But in existing these asymmetric hydrogenation methods, the obvious deficiency of existence is: the slight change of chiral diphosphine ligand on three-dimensional arrangement and stereo-electronic effect causes the activity of ruthenium catalyged precursor and enantioselectivity significantly to reduce usually.
Summary of the invention
The object of the present invention is to provide a kind of method of asymmetric hydrogenation synthesis of chiral secondary alcohol of prochiral ketone.
The present invention realizes through following measure:
The present invention is with phenyl ruthenous chloride and chirality bridging biphosphine ligand (Rax)-BuP and chiral diamine (R; R)-and DPEN prepared in reaction catalyst precursor, be reactant with prochiral ketone, hydrogen, make auxiliary agent with potassium tert.-butoxide; In the low-carbon alcohol solvent, through asymmetric hydrogenation one-step synthesis chiral, secondary alcohols.
A kind of method of asymmetric hydrogenation synthesis of chiral secondary alcohol is characterized in that this method comprises processes successively:
The preparation process of catalyst precursor: under nitrogen protection, phenyl ruthenous chloride and suc as formula chirality bridging biphosphine ligand (the Rax)-BuP shown in the II, mixes 80～120 ℃ of reactions at N in the dinethylformamide solvent; After being cooled to room temperature, (R R)-DPEN, reacts under the room temperature to add chiral diamine shown in formula III; The underpressure distillation solvent adds methylene dichloride dissolved solids thing, concentrates this solution, adds hexane in the liquid concentrator and produces pale brown look deposition, filter, and the filtrate decompression solvent distillation, obtaining the khaki color solid is the ruthenium catalyst precursor;
Formula II (R
Ax)-BuP formula III (R, R)-DPEN
The asymmetric hydrogenation process: under nitrogen protection, ruthenium catalyst precursor and potassium tert.-butoxide are dissolved in the low-carbon alcohol, add the reactant prochiral ketone then, in hydrogen atmosphere, pressure 1～5MPa, 18～28 ℃ of temperature, stirring reaction 18～64 hours; Resultant through rapid column chromatography after concentrating under reduced pressure obtain the product chiral, secondary alcohols.
Reaction-ure conversion-age of the present invention is up to 99wt%, and the product enantioselectivity is up to 92%.
Reaction of the present invention is represented with formula IV:
Formula IV R=H ,-Br ,-CH
3-, or-OCH
3
The compound method of chirality bridging biphosphine ligand (Rax)-BuP is seen document (L. Qiu, A.S.C.Chan, et al J. Am.Chem.Soc., 2006,128 (17), 5955).Chiral diamine (R, R)-DPEN is a commercialization reagent.
Mol ratio between phenyl ruthenous chloride, chirality bridging biphosphine ligand and the chiral diamine is 0.5: 1.1: 1.1～0.45: 1: 1.
The reactant prochiral ketone is selected from contraposition bromoacetophenone, contraposition methyl acetophenone, contraposition methoxyacetophenone, a position bromoacetophenone, a position methyl acetophenone, a position methoxyacetophenone, a kind of in ortho position bromoacetophenone, ortho position methyl acetophenone and the ortho position methoxyacetophenone.
The mole number of prochiral ketone in every liter of low-carbon alcohol is 2.0～5.0.
Low-carbon alcohol is selected from a kind of in methyl alcohol, Virahol and the propyl carbinol.
The mol ratio of ruthenium catalyst precursor and prochiral ketone is 1: 5000～1: 500.
The mol ratio of potassium tert.-butoxide and prochiral ketone is 1: 110～1: 11.
The present invention has following advantage: through the ruthenium catalyst precursor of chirality bridging biphosphine ligand and chiral diamine and phenyl ruthenous chloride prepared in reaction, in air, be not afraid of oxidation, and can weighing in air; The reactant prochiral ketone is cheap and easy to get; Through a step asymmetric hydrogenation, in the 1-5MPa hydrogen pressure, 18-28 ℃ of stirring reaction certain hour, the simple aftertreatment of warp is synthesis of chiral phenylethyl alcohol or substituted benzene ethanol product efficiently.
Embodiment
In order to understand the present invention better, describe through embodiment.
Embodiment 1:
Add phenyl ruthenous chloride ((RuCl in the 100mL Schlenk bottle
2Beneze)
2) (0.05mmol, 25mg), bridging chiral diphosphine ligand (Rax)-BuP (0.105mmol, 64.3mg), N, dinethylformamide 6mL, under nitrogen protection, 100 ℃, stirring reaction.After solution is cooled to room temperature, add chiral diamine (R, R)-DPEN (0.105mmol; 23mg), under this temperature, continue stirring reaction, the underpressure distillation solvent; Add methylene dichloride dissolved solids thing, concentrate this solution, add hexane in the liquid concentrator and produce pale brown look deposition; Filter, the filtrate decompression solvent distillation, obtaining the khaki color solid is the ruthenium catalyst precursor.The ruthenium catalyst precursor
31PNMR (CDCl
3, 202MHz) δ=47.5ppm (s).
Adding ruthenium catalyged precursor in the 100mL Schlenk bottle (0.0025mmol, 2.5mg), potassium tert.-butoxide 0.114mmol, methyl alcohol 1mL; The stirring at room dissolving, (2.5mmol 0.29mL), is transferred to the autoclave that the 30mL band stirs to add methyl phenyl ketone; Hydrogen atmosphere, 2MPa, 20 ℃ of stirring reactions 20 hours.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 46wt%, and product is 55%ee (S)-phenylethyl alcohol.
Embodiment 2:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, Virahol 1mL, stirring at room dissolving, (2.5mmol 0.29mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 2MPa, 28 ℃ of stirring reactions 18 hours to add methyl phenyl ketone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 75%ee (S)-phenylethyl alcohol.
Embodiment 3:
Ruthenium catalyst precursor and number butanols potassium such as embodiment 1, propyl carbinol 1mL, the stirring at room dissolving, (2.5mmol 0.29mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 1MPa, 20 ℃ of stirring reactions 22 hours to add methyl phenyl ketone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 81%ee (S)-phenylethyl alcohol.
Embodiment 4:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 2.2mL, stirring at room dissolving, (7.5mmol 0.81mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 21 hours to add methyl phenyl ketone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 80%ee (S)-phenylethyl alcohol.
Embodiment 5:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 3.5mL, stirring at room dissolving, (12.5mmol 1.45mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 21 hours to add methyl phenyl ketone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 38wt%, and product is 79%ee (S)-phenylethyl alcohol.
Embodiment 6:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 2mL, stirring at room dissolving, (7.5mmol 1.0mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 45 hours to add p-methyl aceto phenone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 80%ee (S)-to methylbenzene ethanol.
Embodiment 7:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 3mL, stirring at room dissolving, (7.5mmol 1.13g), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 40 hours to add p-methoxy-acetophenone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 81%ee (S)-to anisole ethanol.
Embodiment 8:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 3mL, stirring at room dissolving, (7.5mmol 1.49g), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 41 hours to add parabromoacetophenone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 69%ee (S)-to bromobenzene ethanol.
Embodiment 9:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 2.5mL, stirring at room dissolving, (7.5mmol 0.68mL), is transferred to the autoclave that the 30mL band stirs to methyl acetophenone between adding, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 64 hours.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 84%ee (S)-methylbenzene ethanol.
Embodiment 10:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 2.5mL, stirring at room dissolving, (7.5mmol 0.66mL), is transferred to the autoclave that the 30mL band stirs to bromoacetophenone between adding, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 22 hours.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 76%ee (S)-bromobenzene ethanol.
Embodiment 11:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 2.5mL, stirring at room dissolving, (7.5mmol 0.69mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 3MPa, 20 ℃ of stirring reactions 44 hours to add the meta-methoxy methyl phenyl ketone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 84%ee (S)-meta-methoxy phenylethyl alcohol.
Embodiment 12:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 1mL, stirring at room dissolving, (2.5mmol 0.33mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 5MPa, 20 ℃ of stirring reactions 48 hours to add the o-methyl-benzene ethyl ketone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 92%ee (S)-o-methyl-benzene ethanol.
Embodiment 13:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 1mL, stirring at room dissolving, (2.5mmol 0.34mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 5MPa, 20 ℃ of stirring reactions 48 hours to add adjacent bromoacetophenone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 89%ee (S)-adjacent bromobenzene ethanol.
Embodiment 14:
Ruthenium catalyst precursor and potassium tert.-butoxide such as embodiment 1, propyl carbinol 1mL, stirring at room dissolving, (2.5mmol 0.34mL), is transferred to the autoclave that the 30mL band stirs, hydrogen atmosphere, 5MPa, 20 ℃ of stirring reactions 48 hours to add o-methoxyacetophenone.Hydrogen in the emptying still, concentrating under reduced pressure behind the rapid column chromatography, gc records reaction conversion ratio 99wt%, and product is 58%ee (S)-O-methoxy phenylethyl alcohol.
Claims (7)
1. the method for an asymmetric hydrogenation synthesis of chiral secondary alcohol is characterized in that this method comprises processes successively:
The preparation process of catalyst precursor: under nitrogen protection, phenyl ruthenous chloride and suc as formula the chirality bridging biphosphine ligand shown in the II, mixes 80～120 ℃ of reactions at N in the dinethylformamide solvent; After being cooled to room temperature, add the chiral diamine shown in formula III, react under the room temperature; The underpressure distillation solvent adds methylene dichloride dissolved solids thing, concentrates this solution, adds hexane in the liquid concentrator and produces pale brown look deposition, filter, and the filtrate decompression solvent distillation, obtaining the khaki color solid is the ruthenium catalyst precursor;
Formula II (R
Ax)-BuP formula III (R, R)-DPEN
The asymmetric hydrogenation process: under nitrogen protection, ruthenium catalyst precursor and potassium tert.-butoxide are dissolved in the low-carbon alcohol, add the reactant prochiral ketone then, in hydrogen atmosphere, pressure 1～5MPa, 18～28 ℃ of temperature, stirring reaction 18～64 hours; Resultant through rapid column chromatography after concentrating under reduced pressure obtain the product chiral, secondary alcohols.
2. the method for claim 1 is characterized in that the mol ratio between phenyl ruthenous chloride, chirality bridging biphosphine ligand and the chiral diamine is 0.5: 1.1: 1.1～0.45: 1: 1.
3. the method for claim 1; It is characterized in that prochiral ketone is selected from contraposition bromoacetophenone, contraposition methyl acetophenone, contraposition methoxyacetophenone, a position bromoacetophenone, a position methyl acetophenone, a position methoxyacetophenone, a kind of in ortho position bromoacetophenone, ortho position methyl acetophenone and the ortho position methoxyacetophenone.
4. the method for claim 1 is characterized in that the mole number of prochiral ketone in every liter of low-carbon alcohol is 2.0～5.0.
5. the method for claim 1 is characterized in that low-carbon alcohol is selected from a kind of in methyl alcohol, Virahol and the propyl carbinol.
6. the method for claim 1, the mol ratio that it is characterized in that ruthenium catalyst precursor and prochiral ketone is 1: 5000～1: 500.
7. the method for claim 1, the mol ratio that it is characterized in that potassium tert.-butoxide and prochiral ketone is 1: 110～1: 11.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358379A (en) * | 2020-11-09 | 2021-02-12 | 南方科技大学 | Preparation method of optically pure S-configuration 1, 1-bis- (4-fluorophenyl) -2-propanol |
| CN112371192A (en) * | 2021-01-14 | 2021-02-19 | 江苏欣诺科催化剂有限公司 | Composite ruthenium catalyst and preparation method and application thereof |
| CN115448813A (en) * | 2022-10-18 | 2022-12-09 | 中国科学院兰州化学物理研究所 | Method for preparing (S) -2, 6-dichloro-3-fluorophenethyl alcohol |
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| EP0718265A2 (en) * | 1994-12-07 | 1996-06-26 | Research Development Corporation Of Japan | Method for producing an alcohol |
| US20050014633A1 (en) * | 2003-07-11 | 2005-01-20 | Chan Albert Sun-Chi | Biphenyldiphosphine compounds |
| CN101037451A (en) * | 2005-01-27 | 2007-09-19 | 中国科学院上海有机化学研究所 | Transition metal complex, synthesizing method and application in catalytic hydrogenation reaction |
| CN101058532A (en) * | 2006-11-28 | 2007-10-24 | 南开大学 | Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group |
-
2010
- 2010-07-02 CN CN2010102171923A patent/CN102311299A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0718265A2 (en) * | 1994-12-07 | 1996-06-26 | Research Development Corporation Of Japan | Method for producing an alcohol |
| US20050014633A1 (en) * | 2003-07-11 | 2005-01-20 | Chan Albert Sun-Chi | Biphenyldiphosphine compounds |
| CN101037451A (en) * | 2005-01-27 | 2007-09-19 | 中国科学院上海有机化学研究所 | Transition metal complex, synthesizing method and application in catalytic hydrogenation reaction |
| CN101058532A (en) * | 2006-11-28 | 2007-10-24 | 南开大学 | Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group |
Non-Patent Citations (1)
| Title |
|---|
| WEI LI ET AL.: "Highly Efficient and Highly Enantioselective Asymmetric Hydrogenation of Ketones with TunesPhos/1,2-Diamine-Ruthenium(II) Complexes", 《J. ORG. CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358379A (en) * | 2020-11-09 | 2021-02-12 | 南方科技大学 | Preparation method of optically pure S-configuration 1, 1-bis- (4-fluorophenyl) -2-propanol |
| CN112371192A (en) * | 2021-01-14 | 2021-02-19 | 江苏欣诺科催化剂有限公司 | Composite ruthenium catalyst and preparation method and application thereof |
| CN115448813A (en) * | 2022-10-18 | 2022-12-09 | 中国科学院兰州化学物理研究所 | Method for preparing (S) -2, 6-dichloro-3-fluorophenethyl alcohol |
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