CN1331874C - Transition metal complex, synthesis and use thereof - Google Patents
Transition metal complex, synthesis and use thereof Download PDFInfo
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- CN1331874C CN1331874C CNB2005100236320A CN200510023632A CN1331874C CN 1331874 C CN1331874 C CN 1331874C CN B2005100236320 A CNB2005100236320 A CN B2005100236320A CN 200510023632 A CN200510023632 A CN 200510023632A CN 1331874 C CN1331874 C CN 1331874C
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Abstract
The present invention relates to a metallic ruthenium complex compound having the following structural formula and other transitional metal complex compounds, a synthesizing method thereof and a purpose thereof. The synthesizing method is simple and convenient, is suitable for industrialization production, and can be used for catalyzing hydrogenation reaction, particularly for catalyzing asymmetric hydrogenation reaction of acetophenone and the derivant thereof, benzophenone and the derivant thereof, methyl cyclopropyl ketone, gamma-N, N -dimethylamino-alpha-propiophenone and the derivant thereof, and other ketone compounds.
Description
Technical field
The present invention relates to a class transition metal complex, preparation method and use.These metal complexs of synthetic can be used for the reaction of catalysis asymmetric catalytic hydrogenation.This class complex compound can the catalysis methyl phenyl ketone and derivative, benzophenone and derivative thereof, methyl cyclopropyl ketone, γ-N, the asymmetric catalytic hydrogenation reaction of N-dimethylamino-α-Propiophenone and derivative thereof and other ketone compounds.
Background technology
The asymmetric catalytic hydrogenation reaction is focus [Ohkuma, the T. in the current asymmetric synthesis field; Kitamura, M.; Noryori, R. (1999) Asymmetric Hydrogenation.In:Ojiama, I. (ed) CatalyticAsymmetric Synthesis. (2nd Ed.) .Wily-VCH:New York (Englinsh) 2000].Asymmetric catalytic hydrogenation is constantly developed to advancing most several years from the appearance of Wilkinson catalyzer in 1956.The asymmetric hydrogenation of ketone compounds has also had development [Bakos, J.T. rapidly in recent two decades; Heil, B.L.J.Organomet.Chem.1985,279,23], [Jiang, Q.; Jiang, Y.; Xiao, D.; Zhang, X.Angew.Chem.Int.Ed.Engl.1998,37,1100].A breakthrough progress is that Noyori group realizes that they find at complex compound [RuCl
2(S)-BINAP] in, add two amine ligands, can generate a kind of structure is tans-[RuCl
2(phosphane) (1,2-diamine)] complex compound, in the presence of alkali (as t-BuOK or KOH), the asymmetric hydrogenation of catalyzing ketone substrate [Noyori, R. efficiently; Takeshi, O.; Hirohito, O.Shohei, H.; Takao, I.J.Am.Chem.Soc.1995,117,2675], [Noyori, R.; Ohkuma, T.; Douce, H.; Murata, K.; Yokozawa, T.; Kozawa, M.; Katayama, E.; England, A.F.; Ikariya, T., Angew.Chem.Int.Ed.1998,37,1703].In recent years, emerged many chiral diphosphine ligands again, be applied in the asymmetric hydrogenation of ketone compounds, also can obtain extraordinary result [Jing, W.; Hua, C.; Waihim, K.; Rongwei, G.; Zhongyuan, Z.; Chihung, Y.; Chan, S.C., J.Chem.Soc.2002,67,7908], [Jing, W.; Jian, X.; Rongwei, G.; Chihung, Y.; Chan, S.C., Chem.Eur.J.2003,9,2963], [Jian, H.X.; Xin, L.W.; Fu, Y; Shuo, F.Z.; Bao, M.F.; Hai, F.D.; Zhou, Q.L.J.Am.Chem.Soc.2003.125,4404], [Mark, J.; William, H.; Daniela, H.; Christophe, M.; Antonio, Z.G.Org.Lett.2000,26,4173].And recently Mikami group cooperate with Noyori group, will the activatory application of policies not arrived [Okuma, T. in the middle of the asymmetric hydrogenation of ketone substrate; Doucet, H.; Phanm, T.; Mikami, K.; Korenaga, T.; Terada, M.; Noyori, R.J Am.Chem.Soc., 1998,120,1086], [Mikami, K.; Korenaga, T.; Terada, M.; Ohkuma, T.; Pham, T.; Noyori, R.Angew.Chem.Int.Ed.Ehgl., 1999,38,495], also obtained result preferably.Relevant have research [Katayama, E. are also arranged utilizing aspect achiral phosphine part; Inoue, T.JP2001002610,2001], [Ooka, H.; Kanagawa, Inoue, T.WO007506A1,2004], [Suparabhom, S.; Susanne, L.; Chen, W.P.; Xiao J.L J Mole.Catal.A, Chemical 2003,196,125-129].
However, the synthetic difficulty that still compares of the chiral diphosphine ligand that these synthetic these catalyzer are used or the part of racemization, therefore, patent of the present invention will be an object with the asymmetric catalytic hydrogenation reaction, practical catalyst system inexpensive to develop, efficient, highly selective is a target, by new ideas and the combinational chemistry that uses above-mentioned asymmetric activation, develop not only practicality but also asymmetric catalytic hydrogenation system efficiently.
Summary of the invention
The purpose of this invention is to provide a kind of transition metal complex.Such metal complex can be used for the asymmetric catalytic hydrogenation reaction.Especially metal Ru complex compound.
Another object of the present invention provides the synthetic method of above-mentioned transition metal complex.
Purpose of the present invention also provides the application with above-mentioned complex compound.Can be used for the catalysis asymmetric hydrogenation, further describe to being applied to methyl phenyl ketone and derivative thereof, benzophenone and derivative thereof, methyl cyclopropyl ketone, γ-N, the catalytic hydrogenation of N-dimethylamino-α-Propiophenone and derivative thereof and other ketone compounds.The overall texture formula of the transition metal complex that this patent is related is as follows:
Wherein A or B can be R
1R
2R
3P
-, perhaps A and B are
D or E=R
7Or R
8, perhaps D and E=R
13Above-mentioned transition metal complex can be the metal complex of metal complex, biphosphine ligand and monoamine part of metal complex, monophosphorus ligand and the diamine ligand of monophosphorus ligand and monoamine part or the metal complex of biphosphine ligand and diamine ligand.Structural formula also further can be described below:
In all structural formulas, M can be transition metal such as Ru, Pd, Cu or Fe, and X can be chlorine, bromine, iodine.R
9Can be hydrogen, methyl sulphonyl, to Methyl benzenesulfonyl base etc.
R in structural formula C1
1, R
2, R
3, R
4, R
5Or R
6Can be C
2-12Alkyl, described alkyl can be ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, suberyl, phenyl, benzyl, 3, the 5-dimethyl benzyl, 1. naphthyl, 2-naphthyl and
Deng.R
14Or R
15Can distinguish hydrogen, methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, suberyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, phenyl, phenoxy group, methylphenoxy, 3,5-3,5-dimethylphenyl, benzyl, 3,5-dimethyl benzyl and naphthyl etc.
When adopting chirality monoamine part, R
7Or R
8Can for
R
17Can be methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy etc.The absolute configuration of chirality monoamine part both can be the R configuration, also can be the S configuration.
When adopting the chirality diamine ligand, catalyst structure can be expressed as C3 and C4, wherein R respectively
13Can be the following group:
And R wherein
18Or R
19Can be respectively hydrogen, methyl, ethyl, coin propyl group, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, etc.The absolute configuration of chirality diamine ligand both can be (R, R)
Configuration also can be (S, S) configuration.
When adopting biphosphine ligand, catalyst structure can further be expressed as C2 and C3, wherein R
12Can be the following group:
And R wherein
10Or R
11Can be respectively phenyl, p-methylphenyl, 3,5-3,5-dimethylphenyl etc.
The preparation of such complex compound can be under 0 ℃-100 ℃ in organic solvent neutralization reaction temperature, obtained in 0.5～20 hour by transistion metal compound, diamine ligand or monoamine part, biphosphine ligand or monophosphorus ligand reaction, wherein the mol ratio of transistion metal compound, diamine ligand or monoamine part, biphosphine ligand or monophosphorus ligand is 1: 1～5: 1～5, wherein the structural formula of diamine ligand or monoamine part is A and B, and the structural formula of biphosphine ligand or monophosphorus ligand is
With
Wherein A, B, E, D and R
9As previously mentioned.When adopting monoamine or monophosphorus ligand, the mol ratio of transistion metal compound and monoamine or monophosphorus ligand is 1: 3～5, recommends 1: 4; When adopting diamine or biphosphine ligand, the mol ratio of transistion metal compound and diamine or biphosphine ligand is 1: 1～3, recommends 1: 2.Described transistion metal compound is the halogenide of Ru, Pd, Cu or Fe or their complex compound, as [RuX
2(C
6H
6)]
2, RuX
3, PdX
2, CuX
2, FeX
2Deng.
Specifically being represented by following reaction formula, is example with the peg complex compound:
R in the reaction formula
1-R
13Group described as defined above.
The organic solvent that uses in aforesaid method of the present invention can be benzene,toluene,xylene, trimethylbenzene, acetonitrile, ether, tetrahydrofuran (THF), glycol dimethyl ether, trichloromethane, methylene dichloride, methyl alcohol, ethanol, Virahol, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc.
The absolute configuration of the chirality monoamine part that the present invention is used both can be (R) configuration, also can be (S) configuration.The absolute configuration of chirality diamine ligand both can be that (R, R) configuration also can be (S, S) configuration.
The synthetic method of transition metal complex of the present invention is not only easy, be fit to suitability for industrialized production, and can be used for the catalysis asymmetric hydrogenation, be applied to methyl phenyl ketone and derivative thereof, benzophenone and derivative thereof, methyl cyclopropyl ketone, γ-N furtherly, the catalytic hydrogenation of N-dimethylamino-α-Propiophenone and derivative thereof and other ketone compounds.
Specific implementation method
Help further to understand the present invention by following embodiment, but do not limit the content of invention.
Preparation of catalysts
Preparation method of the present invention can be further as follows with the preparation process embodiment of representational compound:
Method one
[(Ph
3P)
2RuCl
2(R, R)-DPEN be prepared as example]
DPEN is 1, the 2-diphenyl ethylene diamine
Embodiment 1: catalyzer 6 (Ph
3P)
2RuCl
2(R, R)-preparation of DPEN
Universal method (method one): under argon shield with 50mg (0.24mmol) RuCl
3With 300mg (1.14mmol) PPh
3Put into reaction tubes, and load onto reflux.Add the anhydrous CH of 12mL
3OH, reflux 5 hours.This moment, the red-brown solid of meeting was separated out, and filtered under argon shield, washed solid with anhydrous diethyl ether, and the decompressing and extracting solvent is directly used in next step reaction.
Under argon shield, above-mentioned Powdered solid 153mg (0.16mmol) is put into reaction tubes, add the anhydrous CH of 2mL
2Cl
2, stir after 10 minutes, and adding 38.2mg (0.18mmol) (R, R)-1, the 2-diphenyl ethylene diamine, stirring is spent the night.Add the 5mL anhydrous n-hexane, can separate out pale brown look solid, under argon shield, filter, use anhydrous CH
2Cl
2And the anhydrous n-hexane recrystallization can get pale brown look crystal 109mg.Productive rate: 75%.M.p.213-215℃(Dec.)；[α]
D 20＝+170.4°(c＝0.45，CHCl
3)；IR(KBr)ν3313cm
-1(N-H)；
1H?NMR(300MHz，CDCl
3)：δ7.53(s，12H)，7.24-7.07(m，24H)，6.85(s，4H)，4.29(t，J＝4.5Hz，2H)，3.70(m，2H)，3.36(s，1H)，3.34(s，lH)；
31P?NMR(121MHz，CDCl
3)：δ46.91ppm。
Embodiment 2: catalyzer 7 (Ph
3P)
2RuCl
2(NH
2CH
2CH
2NH
2)
Employing method one, the first step refluxed 10 hours, productive rate: 74%.
1H?NMR(300MHz，CDCl
3)：δ7.52-7.46(m，12H)，7.29-7.24(m，6H)，7.13(t，J＝7.5Hz，12H)，2.99(br，4H)，2.79(s，4H)；
31P?NMR(121MHz，CDCl
3)：δ44.49ppm。
Embodiment 3: catalyzer 8
Employing method one, the first step refluxed 4 hours, productive rate: 71%.
M.p.234-235℃(Dec.)；[α]
D 20＝+115.5°(c＝0.54，CHCl
3)；IR(KBr)ν3312?cm
-1(N-H)；
1H?NMR(300MHz，CDCl
3)：δ7.17(t，J＝9.9Hz，12H)，7.10-7.07(m，5H)，6.95-6.87(m，5H)，6.80(s，4H)，4.30(t，J＝4.8Hz，2H)，3.69-3.66(m，2H)，3.41(s，1H)，3.39(s，1H)，2.11(s，36H)；
31P?NMR(121MHz，CDCl
3)：δ43.67ppm。
Embodiment 4: catalyzer 9
Productive rate: 80%.
1H?NMR(300MHz，CDCl
3)：δ7.41-7.35(m，12H)，7.16-7.11(m，18H)，6.87-6.84(m，4H)，4.28(t，J＝4.8Hz，2H)，3.61(m，2H)，3.35(s，1H)，3.32(s，1H)；
31P?NMR(121MHz，CDCl
3)：δ44.54ppm。
Embodiment 5: catalyzer 10
Employing method one, the first step are solvent refluxing 15 hours with ethanol, productive rate: 79%.
1H?NMR(300MHz，CDCl
3)：δ7.44-7.39(m，12H)，7.09-7.07(m，6H)，6.90-6.87(m，4H)，6.64(d，J＝5.4Hz，12H)，4.29(t，J＝4.8Hz，2H)，3.74-3.65(m，20H)；
31P?NMR(121MHz，CDCl
3)：δ41.65ppm。
Embodiment 6: catalyzer 11
Productive rate: 62%.
1H?NMR(300MHz，CDCl
3)：δ7.55-7.50(m，12H)，7.20-7.17(m，10H)，7.11-7.06(m，14H)，6.63(d，J＝5.4Hz，2H)，4.67(s，4H)，3.72(s，6H)，3.18(br，2H)；
31P?NMR(121MHz，CDCl
3)：δ44.98ppm。
Embodiment 7: catalyzer 12
Productive rate: 66%.
1H?NMR(300MHz，CDCl
3)：δ7.16-7.13(m，12H)，6.80(s，6H)，6.72(s，2H).6.48(s，4H)，4.22(t，J＝4.5Hz，2H)，3.56(m，2H)，3.34(s，1H)，3.31(s，1H)，2.13(s，12H)，2.05(s，36H)；
31P?NMR(121MHz，CDCl
3)：δ43.71ppm。
Embodiment 8: catalyzer 13
Employing method one, the first step are solvent refluxing 12 hours with ethanol, and second step, the 2-ethylene dichloride was a solvent, reacted 10 hours with 1.Productive rate: 66%.
1H?NMR(300MHz，CDCl
3)：δ7.52-7.49(m，4H)，7.16-7.05(m，20H)，6.89-6.83(m，8H)，4.35(t，J＝4.5Hz，2H)，3.74-3.69(m，2H)，3.46(s，1H)，3.42，(s，1H)，2.32?s，6H)，2.07(s，12H)，2.05(s，12H)；
31P?NMR(121MHz，CDCl
3)：δ43.95ppm。
Embodiment 9: catalyzer 14
Productive rate: 77%.
1H?NMR(300?MHz，CDCl
3)：δ?7.20-7.17(m，12H)，6.79(s，10H)，6.23(d，J＝7.2Hz，4H)，4.23(t，J＝4.5Hz，2H)，3.70(s，6H)，3.61(m，2H)，3.33，(s，1H)，3.3?1(s，1H)，2.04(s，36H)；
31P?NMR(121MHz，CDCl
3)：δ?43.65ppm。
Embodiment 10: catalyzer 15
Employing method one, the first step refluxed 4 hours, and second step is intact with three chloromethanes to be solution, productive rate: 76%.
31P?NMR(121MHz，CDCl
3)：δ?49.93?ppm；
19F?NMR(282MHz，CDCl
3)：δ-63.55ppm。
Embodiment 11: catalyzer 16 (Ph
3P)
2RuCl
2[(S)-BINAM]
BINAM is: 2, and 2 '-dinaphthalene amine
Productive rate: 79%.
1H?NMR(300?MHz，CDCl
3)：δ?7.80(d，J＝8.1Hz，2H)，7.32(d，J＝8.7Hz，2H)，7.58(t，J＝8.4Hz，12H)，7.33-7.27(m，2H)，7.24-7.22(m，6H)，7.15-7.09(m，14H)，6.95(d，J＝8.4Hz，2H)，6.59(d，J＝8.7Hz，2H)，5.24(br，2H)，4.58(br，2H)；
31P?NMR(121?MHz，CDCl
3)：δ?47.25ppm。
Embodiment 12: catalyzer 17
Productive rate: 76%.
1H?NMR(300MHz，CDCl
3)：δ7.30-7.26(m，6H)，7.78-7.76(m，14H)，6.81(s，4H)，6.73(s，2H)，4.27(t，J＝4.2Hz，2H)，3.17(m，2H)，3.39(s，1H)，3.37，(s，1H)，2.20(s，12H)，5.05(s，36H)；
31P?NMR(121MHz，CDCl
3)：δ43.68ppm。
Embodiment 13: catalyzer 18 (Ph
3P)
2RuCl
2[(S, S)-m-CH
3-DPEN]
Productive rate: 70%.
1H?NMR(300MHz，CDCl
3)：δ7.52-7.50(m，14H)，7.23-7.19(m，16H)，6.96-6.91(m，4H)，6.66-6.60(m，4H)，4.23(t，J＝5.4Hz，2H)，3.68(m，2H)，3.32(s，1H)，3.30(s，1H)，2.18(s，6H)；
31P?NMR(121MHz，CDCl
3)：δ45.03ppm。
Embodiment 14: catalyzer 19 (Ph
3P)
2RuCl
2[(R, R)-p-OCH
3-DPEN]
Productive rate: 73%.
1H?NMR(300MHz，CDCl
3)：δ7.53-7.50(m，10H)，7.35-7.33(m，10H)，7.19-7.07(m，10H)，6.76(d，J＝8.7Hz，4H)，6.60(d，J＝8.7Hz，4H)，4.19(t，J＝4.5Hz，2H)，3.72(s，6H)，3.61(br，2H)，3.31(s，1H)，3.28(s，1H)；
31P?NMR(121MHz，CDCl
3)：δ44.98ppm。
Embodiment 15: catalyzer 20 (Ph
3P)
2RuCl
2[(S, S)-p-CH
3-DPEN]
Productive rate: 80%.
1H?NMR(300MHz，CDCl
3)：δ7.52-7.47(m，10H)，7.23-7.18(m，6H)，7.09(t，J＝7.5Hz，12H)，6.87(d，J＝8.1Hz，4H).6.72(d，J＝7.8Hz，4H)，4.23(t，J＝4.5Hz，2H)，3.66(br，2H)，3.33(s，1H)，3.30(s，1H)，2.18(s，6H)；
31P?NMR(121MHz，CDCl
3)：δ44.97ppm。
Embodiment 16: catalyzer 21
Productive rate: 71%.
31P?NMR(121MHz，CDCl
3)：δ46.58ppm。
Embodiment 17: catalyzer 22 (Ph
3P)
2RuCl
2[(S, S)-3,5-Di-CH
3-DPEN]
Productive rate: 73%.
31P?NMR(121MHz，CDCl
3)：δ45.10ppm。
Embodiment 18: catalyzer 23
(Ph
3P)
2RuCl
2[(S)-DAIPEN]
Employing method one, the first step reaction is a solvent with the Virahol, refluxes 7 hours.Productive rate: 67%.
31P?NMR(121MHz，CDCl
3)：δ45.56ppm。
Embodiment 19: the preparation of catalyzer 24
Universal method (method two): under argon shield with 128mg (0.202mmol) biphosphine ligand (or monophosphorus ligand 0.404mmol) and 50mg (0.10mol) [RuCl
2(C
6H
6)]
2Put into reaction tubes.Add the anhydrous N of 2mL, dinethylformamide (DMF) is put into 100 ℃ oil bath, stirs 30 minutes.Reduce to and add 46mg (0.216mmol) after the room temperature (R, R)-DPEN, stirring is spent the night.Reduce pressure then and DMF is taken out (can suitably heat, but temperature being no more than 50 ℃).The anhydrous CH of remaining solid
2Cl
2And the Hexane recrystallization can get red-brown solid 162mg.Productive rate: 84%.
31P?NMR(121MHz，CDCl
3)：δ47.87ppm。
Embodiment 20: catalyzer 25
Adopt N, dinethylformamide is a solvent, and 100 ℃ were reacted 1 hour.Productive rate: 84%.
31P?NMR(121MHz，CDCl
3)：δ47.78，47.59，47.29，47.09ppm。
Embodiment 21: catalyzer 26
Productive rate: 75%.
31P?NMR(121MHz，CDCl
3)：δ47.34?ppm。
Embodiment 22: catalyzer 27
Adopt N, dinethylformamide is a solvent, and 100 ℃ were reacted 2 hours.Productive rate: 86%.
M.p.183-185℃；[α]
20 D＝+53.1°(c＝0.91，CHCl
3)；IR(KBr)v?3315?cm
-1(N-H)；
1HNMR(300MHz，CDCl
3)：δ8.09-8.06(m，12H)，7.42(s，6H)，7.31-7.25(m，26H)，7.19-7.12(m，34H)，7.03(t，J＝7.2Hz，2H)，6.92(t，J＝7.5Hz，4H)，6.79(d，J＝7.5Hz，4H)，4.45(m，2H)，4.12-4.15(m，2H)，3.67(br，2H)；
31P?NMR(121MHz，CDCl
3)：δ50.95ppm。
Embodiment 23: catalyzer 28
Adopt N, dinethylformamide is a solvent, and 100 ℃ were reacted 3 hours.Productive rate: 81%.
M.p.177-179℃；[α]
20 D＝+57.4°(c＝1.07，CHCl
3)；IR(KBr)ν3313cm
-1(N-H)；
1HNMR(300MHz，CDCl
3)：δ8.07-7.98(m，12H)，7.37(s，6H)，7.02-6.84(m，32H)，6.76(s，16H)，4.43(br，2H)，4.01-3.97(m，2H)，3.61(br，2H)，2.11(s，36H)；
31P?NMR(121?MHz，CDCl
3)：δ51.12ppm。
Embodiment 24: catalyzer 29 (Ph
3P)
2RuCl
2
Productive rate: 87%.
31P?NMR(121MHz，CDCl
3)：δ27.80ppm.
Embodiment 25: catalyzer 30 (Ph
3P)
2RuCl
2[(R)-NH
2(CH
3) CHPh]
2
Productive rate: 88%.
31P?NMR(121MHz，CDCl
3)：δ37.83ppm。
Embodiment 26: catalyzer 31
Productive rate: 73%.
31P?NMR(121MHz，CDCl
3)：δ43.79ppm。
Embodiment 27: catalyzer 32
Productive rate: 72%.
31PNMR(121MHz，CDCl
3)：δ44.13ppm。
Embodiment 28: catalyzer 33
Productive rate: 84%.
31P?NMR(121MHz，CDCl
3)：δ43.45ppm。
Embodiment 29: catalyzer 34
Productive rate: 82%.
31P?NMR(121MHz，CDCl
3)：δ44.47ppm。
Embodiment 30: catalyzer 35
Productive rate: 80%.
31P?NMR(121MHz，CDCl
3)：δ28.52ppm。
Embodiment 31: catalyzer 36
Productive rate: 79%.
31P?NMR(121MHz，CDCl
3)：δ36.93ppm.
Embodiment 32: catalyzer 37[(S)-BINAP] RuCl
2(NH
2CH
2CH
2NH
2)
Productive rate: 87%.
31P?NMR(121MHz，CDCl
3)：δ45.93ppm。
Embodiment 33: catalyzer 38 (Ph
3P)
2RuCl
2[(R, R)-TsDPEN]
N-p-toluenesulfonyl-1, the 2-diphenyl ethylene diamine
Productive rate: 85%.
31P?NMR(121MHz，CDCl
3)：δ27.20ppm。
Embodiment 34: catalyzer 39
Productive rate: 77%.
31P?NMR(121MHz，CDCl
3)：δ27.84ppm。
Embodiment 35: catalyzer 40
Productive rate: 79%.
31P?NMR(121MHz，CDCl
3)：δ45.11ppm。
Embodiment 36: catalyzer 41
The employing N,N-dimethylacetamide is a solvent, and 100 ℃ were reacted 1 hour.Productive rate: 85%.
31P?NMR(121MHz，CDCl
3)：δ173.9ppm。
Embodiment 37: catalyzer 42
The employing N,N-dimethylacetamide is a solvent, and 100 ℃ were reacted 1 hour.Productive rate: 86%.
31P?NMR(121MHz，CDCl
3)：δ173.6ppm。
Embodiment 38: catalyzer 43
DACH is 1, the 2-cyclohexanediamine, and the employing N,N-dimethylacetamide is a solvent, 100 ℃ were reacted 4 hours
Productive rate: 87%.
31P?NMR(121MHz，CDCl
3)：δ31.02ppm。
Embodiment 39: catalyzer 44 (Ph
3P)
2RuCl
2[(R, R)-DACH]
Productive rate: 87%.
31P?NMR(121MHz，CDCl
3)：δ44.82ppm。
Embodiment 40: catalyzer 45 (Ph
3P)
2PdCl
2[(R, R)-DPEN]
Under argon shield with 106mg (0.404mmol) PPh
3And 35mg (0.20mol) PdCl
2Put into reaction tubes.Add the 2mL dry toluene, put into 110 ℃ oil bath, stirred 5 hours.Reduce to and add 45mg (0.21mmol) after the room temperature (R, R)-DPEN, stirring is spent the night.Reduce pressure then and toluene is taken out (can suitably heat, but temperature being no more than 50 ℃).The anhydrous CH of remaining solid
2Cl
2And the Hexane recrystallization can get yellow solid 155mg.Productive rate: 85%.
31P?NMR(121MHz，CDCl
3)：δ22.40ppm。
Embodiment 41: catalyzer 46 (Ph
3P)
2CuCl
2[(S, S)-DPEN]
Under argon shield with 106mg (0.404mmol) PPh
3And 34 mg (0.20mol) CuCl
22H
2O puts into reaction tubes.Add 2mL anhydrous dimethyl benzene, put into 110 ℃ oil bath, stirring reaction 7 hours.Reduce to and add 45mg (0.21mmol) after the room temperature (R, R)-DPEN, stirring is spent the night.Reduce pressure then and dimethylbenzene is taken out (can suitably heat, but temperature being no more than 50 ℃).The anhydrous CH of remaining solid
2Cl
2And the Hexane recrystallization can get green solid 145mg.Productive rate: 83%.
31P?NMR(121MHz，CDCl
3)：δ36.47ppm。
Embodiment 42: catalyzer 47 (Ph
3P)
2FeCl
2[(S, S)-DPEN]
Under argon shield with 106mg (0.404mmol) PPh
3And 40mg (0.20mol) FeCl
22H
2O puts into reaction tubes.Add the 2mL anhydrous dimethyl sulfoxide, put into 100 ℃ oil bath, during stirring reaction 15.Reduce to and add 45mg (0.21mmol) after the room temperature (R, R)-DPEN, stirring is spent the night.Reduce pressure then and methyl-sulphoxide is taken out (can suitably heat, but temperature being no more than 70 ℃).The anhydrous CH of remaining solid
2Cl
2And the Hexane recrystallization can get red solid 130mg.Productive rate: 75%.
31P?NMR(121MHz，CDCl
3)：δ44.82ppm。
Embodiment 43: catalyzer 48
The employing N,N-dimethylacetamide is a solvent, and 100 ℃ were reacted 5 hours.Productive rate: 87%.
31P?NMR(121MHz，CDCl
3)：δ45.86ppm。
Embodiment 44: catalyzer 49
Productive rate: 85%.
31P?NMR(121MHz，CDCl
3)：δ43.78ppm。
Embodiment 45: catalyzer 50
Productive rate: 88%.
31P?NMR(121MHz，CDCl
3)：δ42.37ppm。
Embodiment 46: catalyzer 51
Productive rate: 83%.
31P?NMR(121MHz，CDCl
3)：δ43.46ppm。
Embodiment 47: catalyzer 52
The employing dimethyl sulfoxide (DMSO) is a solvent, and 100 ℃ were reacted 5 hours.Productive rate: 79%.
31P?NMR(121MHz，CDCl
3)：δ44.69ppm。
Catalytic hydrogenation
Embodiment 48: the asymmetric hydrogenation of phenyl ethyl ketone (I):
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 240mg (2.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20 normal atmosphere (atm) pressure stirred under the room temperature after 5 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.5%.[α]
D 20=-53.7 ° of (c=0.87, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (SuplcoBETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 49: the asymmetric hydrogenation of phenyl ethyl ketone (II):
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 2.40g (20mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.1%; [α]
20 D=-53.6 ° of (c=0.90, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (SuplcoBETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; T (R), 14.7min; T (S), 15.2min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 50: the asymmetric hydrogenation of phenyl ethyl ketone (III):
Under argon shield, in the reaction tubes of an existing magneton, add 2.7mg (0.003mmol) catalyzer 6 and 6.7mg (0.06mmol) t-BuOK, the 2.0mL anhydrous isopropyl alcohol is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 360mg (3.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 6 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 75.5%.
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is the S configuration.
Embodiment 51: the asymmetric hydrogenation of phenyl ethyl ketone (IV):
Under argon shield, in the reaction tubes of an existing magneton, add 3.2mg (0.003mmol) catalyzer 8 and 6.7mg (0.06mmol) t-BuOK, the 2.0mL anhydrous isopropyl alcohol is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 360mg (3.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 10atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 87.0%.
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is the S configuration.
Embodiment 52: the asymmetric hydrogenation of phenyl ethyl ketone (V):
Under hydrogen shield, in the reaction tubes of an existing magneton, add 3.5mg (0.003mmol) catalyzer 15 and 5.7mg (0.06mmol) t-BuONa, the 2.0mL anhydrous isopropyl alcohol is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 360mg (3.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 8 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 77.1%.
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is the S configuration.
Embodiment 53: the asymmetric hydrogenation of phenyl ethyl ketone (VI):
Under argon shield, in the reaction tubes of an existing magneton, add 3.0mg (0.003mmol) catalyzer 25 and 3.3mg (0.06mmol) KOH, the 3.0mL anhydrous isopropyl alcohol is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 360mg (3.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 81.5%.
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is the S configuration.
Embodiment 54: the asymmetric hydrogenation of phenyl ethyl ketone (VII):
Under argon shield, in the reaction tubes of an existing magneton, add 3.9mg (0.005mmol) catalyzer 49 and 4.0mg (0.10mmol) NaOH, the anhydrous n-propyl alcohol of 5.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 360mg (3.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 12 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 75.5%.
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is the S configuration.
Embodiment 55: the asymmetric hydrogenation of phenyl ethyl ketone (VIII):
Under argon shield, in the reaction tubes of an existing magneton, add 4.1mg (0.005mmol) catalyzer 48 and 4.0mg (0.10mmol) NaOH, the anhydrous n-propyl alcohol of 5.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 360mg (3.0mmol) phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 40atm pressure stirred under the room temperature after 16 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get the 1-phenylethyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 75.5%.
1H NMR (300MHz, CDCl
3) δ 7.34-7.32 (m, 5H), 4.82 (q, J=9.6Hz, 1H), 2.61 (br, 1H), 1.44 (d, J=4.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 120 ℃; Retention time t (R), 14.7min; T (S), 15.2min, absolute configuration is the R configuration.
The asymmetric hydrogenation of embodiment 56:4 '-aminomethyl phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 30 minutes after, add 268mg (2.0mmol) 4 '-aminomethyl phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 4 '-aminomethyl phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 93.7%, [α]
D 20=-52.1 ° of (c=0.89, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.28 (d, J=7.8Hz, 2H), 7.18 (d, J=7.8Hz, 2H), 4.87 (q.J=9.6Hz, 1H), 2.35 (s, 3H), 1.88 (br, 1H), 1.50 (d, J=6.3Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 135 ℃; T (R), 11.7min; T (S), 12.2min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 57:2 '-aminomethyl phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 268mg (2.0mmol) 2 '-aminomethyl phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 7 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-aminomethyl phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.1%; [α]
D 20=-72.5 ° of (c=0.75, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.50 (d, J=7.8Hz, 1H), 7.24-7.29 (m, 3H), 5.09 (q, J=6.3Hz, 1H), 2.32 (s, 3H), 2.11 (br, 1H), 1.44 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mmi.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 135 ℃; T (R), 14.2min; T (S), 15.8min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 58:2 '-p-methoxy-phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 300mg (2.0mmol) 2 '-p-methoxy-phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-p-methoxy-phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 93.3%; [α]
D 20=-23.4 ° of (c=0.79, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.36-7.33 (m, 1H), 7.28-7.22 (m, 1H), 6.99 (t, J=7.2Hz, 1H), 6.87 (d, J=8.1Hz, 1H), 5.12 (q, J=6.0Hz, 1H), 3.89 (s, 3H), 1.52 (d, J=6.1Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 135 ℃; T (S) .17.6min; T (R), 18.7min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 59:4 '-p-methoxy-phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 268mg (2.0mmol) 4 '-p-methoxy-phenyl ethyl ketone again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 40atm pressure stirred under the room temperature after 2 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 4 '-p-methoxy-phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 87.9%.[α]
D 20=-44.6 ° of (c=0.85, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.31 (d, J=9.0Hz, 2H), 6.89 (d, J=9.0Hz, 2H), 4.87 (q, J=6.3Hz, 1H), 3.78 (s, 3H), 1.99 (br, 1H), 2.1 1 (br, 1H), 1.44 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 0.8mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 140 ℃; T (R), 27.0min; T (S), 27.8min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 60:2 '-bromo phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 400mg (2.0mmol) 2 '-bromo phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-bromo phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 96.1%.[α]
D 20=-52.1 ° of (c=0.93, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.61 (d, J=8.1Hz, 1H), 7.52 (d, J=8.1Hz, 1H), 7.34 (t, J=15.3Hz, 1H), 7.13 (t, J=15.0Hz, 1H), 5.24 (q, J=9.6Hz, 1H), 1.49 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.2mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 140 ℃; T (R), 13.0min; T (S), 14.9min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 61:3 '-bromo phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 400mg (2.0mmol) 3 '-bromo phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 4 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 3 '-bromo phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 93.3%; [α]
D 20=-29.3 ° of (c=0.96, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.52 (s, 1H), 7.41-7.37 (m, 1H), 7.29-7.17 (m, 2H), 4.87 (q, J=6.3Hz, 1H), 2.20 (br, 1H), 1.50 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mmi.d. * 30m); Carrier gas is N
2(flow velocity is 1.1mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 150 ℃; T (R), 18.9min; T (S), 19.3min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 62:4 '-bromo phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 400mg (2.0mmol) 4 '-bromo phenyl ethyl ketone again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 3 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 4 '-bromo phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 80.5%; [α]
D 20=-25.2 ° (c=0.83, CHOH);
1H NMR (300MHz, CDCl
3) δ 7.49 (d, J=9.0Hz, 2H), 7.46 (d, J=9.0Hz, 2H), 4.90 (q, J=6.6Hz, 1H), 1.88 (br, 1H), 1.48 (d, J=6.3Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.1mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 155 ℃; T (R), 16.4min; T (S), 17.1min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 63:2 '-chlorophenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the 2.0mL anhydrous normal butyl alcohol is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 310mg (2.0mmol) 2 '-chlorophenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-chlorophenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 96.3%; [α]
D 20=-60.3 ° of (c=0.80, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.59 (d, J=7.8Hz, 1H), 7.33-7.22 (m, 2H), 7.21-7.17 (m, 1H), 5.29 (q, J=6.3Hz, 1H), 2.20 (br, 1H), 1.50 (d, J=4.5Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.2mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 155 ℃; T (R), 8.4min; T (S), 9.2min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 64:3 '-chlorophenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 30 minutes after, add 310mg (2.0mmol) 3 '-chlorophenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 40atm pressure stirred under the room temperature after 13 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 3 '-chlorophenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.3%; [α]
D 20=40.0 ° of (c=0.60, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.36 (s, 1H), 7.29-7.19 (m, 3H), 4.87 (q, J=6.6Hz, 1H), 1.47 (d, J=8.1Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.2mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 140 ℃; T (R), 17.0min; T (S), 17.5min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 65:4 '-chlorophenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 310mg (2.0mmol) 4 '-chlorophenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 4 '-chlorophenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 84.7%; [α]
D 20=-28.2 ° of (c=0.75, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.31 (m, 4H), 4.88 (q, J=6.6Hz, 1H), 1.48 (d, J=5.7Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.2mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 145 ℃; T (R), 14.6min; T (S), 15.3min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 66:2 '-fluoro phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3 mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, gas injects the anhydrous n-propyl alcohol of 2.0mL with ammonia displacement three times in the bottle.Stir made solid dissolving in 20 minutes after, add 278mg (2.0mmol) 2 '-fluoro phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 20 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-fluoro phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.1%; [α]
D 20=-38.2 ° of (c=0.92, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.51-7.45 (m, 1H), 7.28-7.19 (m, 1H), 7.17-7.11 (m, 1H), 7.04-6.98 (m, 1H), 4.87 (q, J=6.3Hz, 1H), 2.36 (br, 1H), 1.53 (d, J=6.0Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 125 ℃; T (R), 12.1min; T (S), 12.8min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 67:4 '-fluoro phenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 280mg (2.0mmol) 4 '-fluoro phenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 4 '-fluoro phenyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 91.5%; [α]
D 20=.-42.5 ° of (c=0.91, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.33-7.26 (m, 2H), 7.05-6.97 (m, 2H), 4.88 (q, J=6.3 Hz, 1H), 2.32 (br, 1H), 1.46 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.1mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 125 ℃; T (R), 12.7min; T (S), 13.4min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 68:2 '-trifluoromethyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 378mg (2.0mmol) 2 '-trifluoromethyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 9 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-trifluoromethyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 96.5%; [α]
D 20=-43.4 ° of (c=0.74, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.82 (d, J=7.8Hz, 1H), 7.61-7.55 (m, 2H), 7.38-7.33 (m, 1H), 5.34 (q, J=6.0Hz, 1H), 2.25 (br, 1H), 1.47 (d, J=6.3Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 130 ℃; T (R), 8.7min; T (S), 9.5min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 69:3 ', the asymmetric hydrogenation of 5 '-two trifluoromethyl ethyl ketones:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 515mg (2.0mmol) 3 ', 5 '-two trifluoromethyl ethyl ketones with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 3 ', 5 '-two trifluoromethyls-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 90.9%; [α]
D 20=-20.0 ° of (c=0.79, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.84 (s, 2H), 7.79 (s, 1H), 5.06 (q, J=3.0Hz, 1H), 2.00 (br, 1H), 1.56 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 125 ℃; T (S), 7.0min; T (R), 7.6min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 70:1 '-naphthyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, 2.0mL anhydrous normal butyl alcohol and 5 μ L Et are injected in gas argon replaces three times in the bottle
3N.Stir made solid dissolving in 20 minutes after, add 340mg (2.0mmol) 1 '-naphthyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 15 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 1 '-naphthyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 94.7%; [α]
D 20=-57.4 ° of (c=0.86, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 8.11-8.08 (m, 1H), 7.89-7.86 (m, 1H), 7.79 (d, J=8.1Hz, 1H), 7.68 (d, J=6.9Hz, 1H), 7.55-7.45 (m, 3H), 7.38-7.33 (m, 1H), 5.68 (q, J=6.6Hz, 1H), 2.18 (br, 1H), 1.66 (d, J=7.2Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 175 ℃; T (S), 23.2min; T (R), 24.0min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 71:2 '-naphthyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, 2.0mL anhydrous normal butyl alcohol E and 5 μ L Et are injected in gas argon replaces three times in the bottle
3N.Stir made solid dissolving in 20 minutes after, add 340mg (2.0mmol) 2 '-naphthyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-naphthyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 90.5%; [α]
D 20=-47.2 ° of (c=0.82, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.86-7.83 (m, 4H), 7.53-7.46 (m, 3H), 3.51 (q, J=7.0Hz, 1H), 1.61 (d, J=6.0Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 170 ℃; T (R), 32.2min; T (S), 32.7min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 72: the asymmetric hydrogenation of ferrocenyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, 2.0mL anhydrous normal butyl alcohol and 5 μ L Et are injected in gas argon replaces three times in the bottle
3N.Stir made solid dissolving in 20 minutes after, add 460mg (2.0mmol) ferrocenyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get ferrocenyl-1-ethanol.Through liquid-phase chromatographic analysis, the enantiomeric excess of product is 87.5%; [α]
D 20=+26.1 ° of (c=0.77, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 4.58 (q, J=6.0Hz, 1H), 4.21-4.18 (m, 9H), 1.46 (d, J=6.6Hz, 3H); High performance liquid chromatography (the Chiralpak Japan AS-H of DaCheng Co., Ltd chiral column, λ=254nm; Flow velocity: 0.7mL/min, normal hexane: Virahol=95: 5; T (S)=16.9min; T (R)=24.4min); The product absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 73:2 '-furyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 220mg (2.0mmol) 2 '-furyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 4 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-furyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 89.5%; [α]
D 20=-9.1 ° of (c=1.56, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.38-7.37 (m, 1H), 6.34-6.32 (m, 1H), 6.24-6.23 (m, 1H), 4.90 (q, J=6.3Hz, 1H), 1.56 (d, J=6.3Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.2mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 95 ℃; T (R), 13.2 min; T (S), 13.5min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 74:2 '-thienyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 255mg (2.0mmol) 2 '-thienyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-thienyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.9%; [α]
D 20=-29.1 ° of (c=0.74, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.29-7.26 (m, 1H), 7.02-6.98 (m, 2H), 5.18 (q, J=6.3Hz, 1H), 2.36 (br, 1H), 1.63 (d, J=6.3Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.2mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 115 ℃; T (R), 18.3min; T (S), 19.1min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 75:2 '-pyridyl ethyl ketone:
Under argon shield; in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK; 4.6 μ L (0.02mmol) triisopropyl boric acid esters and the anhydrous n-propyl alcohol of 2.0mL are injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 244mg (2.0mmol) 2 '-pyridyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 8 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 2 '-pyridyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 80.7%; [α]
D 20=-47.4 ° (c=0.78, EtOH);
1H NMR (300MHz, CDCl
3) δ 8.54 (d, J=5.1Hz, 1H), 7.72-7.64 (m, 1H), 7.30 (d, J=7.8Hz, 1H), 7.21 (m, 1H), 4.89 (q, J=6.6Hz, 1H), 1.52 (d, J=6.6Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.1mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 105 ℃; T (R), 23.1min; T (S), 23.5min, absolute configuration is by measuring [α]
DBe the S configuration.
The asymmetric hydrogenation of embodiment 76:3 '-pyridyl ethyl ketone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the 2.0mL anhydrous normal butyl alcohol is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 244mg (2.0mmol) 3 '-pyridyl ethyl ketone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get 3 '-pyridyl-1-ethanol.Through gas chromatographic analysis, the enantiomeric excess of product is 95.5%; [α]
D 20=-42.9 ° (c=0.76, EtOH);
1H NMR (300MHz, CDCl
3) δ 8.53 (s, 1H), 8.46-8.44 (m, 1H), 7.76-7.72 (m, 1H), 7.30-7.26 (m, 1H), 4.95 (q, J=6.6Hz, 1H), 2.00 (br, 1H), 1.52 (d, J=6.9Hz, 3H); Gas-chromatography (Suplco BETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 140 ℃; T (R), 15.1min; T (S), 15.5min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 77: the asymmetric hydrogenation of phenyl-acetone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 268mg (2.0mmol) phenyl-acetone with syringe again, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 20atm pressure stirred under the room temperature after 5 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get phenyl-1-propyl alcohol.Through gas chromatographic analysis, the enantiomeric excess of product is 96.3%; [α]
D 20=-46.0 ° of (c=1.00, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.35-7.28 (m, 5H), 4.58 (t, J=6.0Hz, 1H), 1.82-1.74 (m, 2H), 0.91 (t, J=7.5Hz, 3H); Gas-chromatography (SuplcoBETA-DEX
TM120, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.0mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 125 ℃; T (S), 18.5min; T (R), 19.0min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 78: γ-N, and the asymmetric hydrogenation of N dimethylamino-α-Propiophenone:
Under argon shield, in the reaction tubes of an existing magneton, add 4.3mg (0.002mmol) catalyzer 28 and 4.5mg (0.04mmol) t-BuOK, the anhydrous n-propyl alcohol of 2.0mL is injected in gas argon replaces three times in the bottle.Stir made solid dissolving in 20 minutes after, add 356mg (2.0mmol) γ-N with syringe again, N-dimethylamino-α-Propiophenone, and seal with soft rubber ball.In with the glove box of nitrogen protection, the soft rubber ball on the reaction flask is opened; and reaction flask is transferred in the autoclave; after sealing, shifts out by autoclave glove box; with high-purity hydrogen with the careful displacement of the nitrogen in the autoclave four times after; the hydrogen that adds 30atm pressure stirred under the room temperature after 10 hours, after the hydrogen in the autoclave is bled off; after the removal of solvent under reduced pressure, be greater than 99% with the magnetic resonance detection feed stock conversion.The liquid remaining reaction filters with the long silicagel column of 10cm, and developping agent is an ethyl acetate: sherwood oil 10: 1 can get γ-N, N-dimethylamino-α-phenylpropyl alcohol.Through liquid-phase chromatographic analysis, the enantiomeric excess of product is 96.7%; [α]
D 20=-21.0 ° of (c=0.91, CHCl
3);
1H NMR (300MHz, CDCl
3) δ 7.40-7.24 (m, 5H), 4.96 (q, J=4.5Hz, 1H), 2.66-2.62 (m, 1H), 2.51-2.45 (m, 1H), 2.31 (s, 6H), 1.86-1.81 (m, 2H); High performance liquid chromatography (the Chiralcel Japan OD-H of DaCheng Co., Ltd chiral column, λ=254nm; Flow velocity: 1.0mL/min, normal hexane: Virahol=95: 5; T (R)=4.5min; T (S)=6.2min); The product absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 79: the asymmetric hydrogenation of cyclopropyl ethyl ketone:
Under argon shield; in the 300mL autoclave body of an existing magneton, add 3.5mg (0.0035mmol) catalyzer 6 and 35mg (0.625mmol) NaOH; gas argon replaces three times in the bottle; after injecting the 5.0mL anhydrous methanol, add 29.5g (350mmol) cyclopropyl ethyl ketone with syringe again.After autoclave sealed, with high-purity hydrogen with the careful displacement of the argon gas in the autoclave four times after, add the hydrogen of 50atm pressure, stir under the room temperature after 24 hours, after the hydrogen in the autoclave is bled off, be greater than 99% with the magnetic resonance detection feed stock conversion.After the reactant distillation, can get cyclopropyl-1-ethanol 28 grams, yield: 95%.Enantiomeric excess through the gas chromatographic analysis product is 30.3%.[α]
D 20=-7.0 ° of (c=1.00, CHCl
3);
1H NMR (300MHz, CDCl
3): δ 3.17-3.04 (m, 1H), 1.29 (d, J=6.3Hz, 3H), 0.94-0.88 (m, 1H), 0.53-0.49 (m, 2H), 0.35-0.31 (m, 1H), 0.22-0.17 (m, 1H); Gas-chromatography (Suplco BETA-DEX
TM325, df=0.25 μ m, 0.25mm i.d. * 30m); Carrier gas is N
2(flow velocity is 1.3mL/min); Injector temperature is 250 ℃; Detector temperature is 300 ℃; Column temperature is 50 ℃; T (S), 12.5min; T (R), 12.9min, absolute configuration is by measuring [α]
DBe the S configuration.
Embodiment 80: the hydrogenation of diphenylmethanone:
Under argon shield; in the 300mL autoclave body of an existing magneton, add 5mg (0.0055mmol) catalyzer 6 and 91mg (1.63mmol) KOH and 100g (550mmol) diphenylmethanone; gas injects the 180mL anhydrous isopropyl alcohol with after the argon replaces three times in the bottle.After autoclave sealed, with high-purity hydrogen with the careful displacement of the argon gas in the autoclave four times after, add the hydrogen of 70atm pressure, stir under the room temperature after 24 hours, after the hydrogen in the autoclave is bled off, be greater than 99% with the magnetic resonance detection feed stock conversion.After solvent removed, can get diphenyl-carbinol 94 grams, yield: 94%.
1H?NMR(300MHz，CDCl
3)：67.36-7.32(m，10H)，5.80(s，1H)
Embodiment 81:4, the hydrogenation of 4 '-difluorodiphenyl base ketone:
Under argon shield; in the 1L autoclave body of an existing magneton, add 8.3mg (0.009mmol) catalyzer 6 and 410mg (3.65mmol) t-BuOK and 100g (458mmol) 4; 4 '-difluorodiphenyl base ketone; gas is with after the argon replaces three times in the bottle; inject the 450mL anhydrous isopropyl alcohol.After autoclave sealed, with high-purity hydrogen with the careful displacement of the argon gas in the autoclave four times after, add the hydrogen of 80atm pressure, stir under the room temperature after 24 hours, after the hydrogen in the autoclave is bled off, be greater than 99% with the magnetic resonance detection feed stock conversion.After solvent removed, underpressure distillation can get 4,4 '-difluorodiphenyl base methyl alcohol, 90 grams, yield: 90%.
1H?NMR(300MHz，CDCl
3)：δ7.33-7.29(m，4H)，7.05-7.00(m，4H)，5.79(s，1H)。
Explanation to above-mentioned asymmetric hydrogenation:
Employed solvent can be methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, positive alcohol, benzene,toluene,xylene, trimethylbenzene, acetonitrile, ether, tetrahydrofuran (THF), glycol dinitrate fan, chloroform, methylene dichloride, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc. in the above-mentioned asymmetric H-H reaction.
Used alkali can be sodium hydroxide, potassium hydroxide, carbonate, supercarbonate, phosphoric acid salt, hydrophosphate, dihydrogen phosphate, fluoride salt, sodium hydride, potassium hydride KH, hydrolith, triethylamine, diisopropyl ethyl amine, Tetramethyl Ethylene Diamine, N, accelerine, N, N-Diethyl Aniline, 1,4-diazabicylo [2,2,2] octane (DABCO), diazabicylo dodecane (DBU), 1,4-lupetazin, 1-methyl piperidine, 1-methylpyrrole, quinoline or pyridine etc.
Adopt the pressure of hydrogen can be 5-80atm, the reaction times can be 2-48 hour.
Claims (6)
1. transition metal complex has following structural formula:
Wherein M is Ru, Pd, Cu or Fe; X is chlorine, bromine, iodine; R
9Be hydrogen, methyl sulphonyl or to the Methyl benzenesulfonyl base; R
1, R
2, R
3, R
4, R
5Or R
6Be ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, suberyl, benzyl, 3,5-dimethyl benzyl, 1-naphthyl or
R
14Or R
15Be hydrogen, methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, suberyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, phenyl, phenoxy group, methylphenoxy, 3,5-3,5-dimethylphenyl, benzyl, 3,5-dimethyl benzyl or naphthyl, R
7Or R
8Be
R
17Be methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy.
2. the synthetic method of a kind of transition metal complex as claimed in claim 1, it is characterized in that in organic solvent neutralization reaction temperature be under 0 ℃-100 ℃, transistion metal compound, monoamine part, monophosphorus ligand reaction obtained in 0.5～20 hour, wherein the mol ratio of transistion metal compound, monoamine part, monophosphorus ligand is 1: 1～5: 1～5, and the structural formula of described monoamine part is R
8-NH
2With
The structural formula of described monophosphorus ligand is R
1R
2R
3P and R
4R
5R
6P, wherein R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8And R
9According to claim 1, described transistion metal compound is the halogenide of Ru, Pd, Cu or Fe or their complex compound.
3. the synthetic method of a transition metal complex as claimed in claim 2, the mol ratio that it is characterized in that described transistion metal compound and monoamine or monophosphorus ligand is 1: 3～5.
4. the synthetic method of transition metal complex as claimed in claim 2 is characterized in that described transistion metal compound is [RuX
2(C
6H
6)]
2, RuX
3, PdX
2, CuX
2Or FeX
2, described X is a halogen.
5. the purposes of a transition metal complex as claimed in claim 1 is characterized in that described transition metal complex is used for the catalysis asymmetric hydrogenation.
6. the purposes of transition metal complex as claimed in claim 5, it is characterized in that described transition metal complex is used for methyl phenyl ketone and derivative, benzophenone and derivative thereof, methyl cyclopropyl ketone, γ-N, the catalytic hydrogenation of N-dimethylamino-α-Propiophenone and derivative thereof and other ketone compounds.
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