CN100408587C - Chiral phosphine thiourea compound, synthesis method and its application - Google Patents
Chiral phosphine thiourea compound, synthesis method and its application Download PDFInfo
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Abstract
The present invention relates to a new-type chiral phosphonothiourea compound, its synthesis method and application. Said invention provides the chemical structure formula of said compound. Said compound can be used as catalyst in asymmetric catalytic Baylis-Hillman reaction. Under the condition of room temperature said compound can be used for catalyzing Baylis-Hillman reaction of sulfimine and various activated olefin hydrocarbons, and can obtain high yield and ee value.
Description
Technical field
The present invention relates to the application in the Baylis-Hillman of asymmetry catalysis reaction of a kind of novel chiral phosphine thiourea compound, synthetic method and this compound thereof.
Background technology
The Baylis-Hillman reaction was reported (Baylis, A.B. first by Baylis and Hillman in one piece of patent in 1972; Hillman, M.E.D.Ger.Offen., 1972,2,155,113; Chem.Abstr.1972,77,34174q; Hillman, M.E.D.; Baylis, A.B.U.S.Patent, 1973,3,743,669).It is meant the α position of active olefin and contains electron deficiency sp
2The electrophilic reagent of type under the effect of catalyzer such as tertiary amine, form carbon-carbon bond reaction (Ciganek, E.Org.React.1997,51,201-350).1), reaction raw materials is cheap and easy to get Baylis-Hillman reaction has following characteristics:.As raw materials such as aldehyde and acrylate industrial all be scale operation; 2), this reaction has Atom economy.Can see also that from reaction formula all atoms of Baylis-Hillman reaction raw materials have all changed into final product; 3), the product of reaction generation has a plurality of functional groups that can further transform.As aldehyde and acrylate reactions, the product of generation has functional groups such as ester group, thiazolinyl and hydroxyl simultaneously; 4), catalyst for reaction is the organic reagent with strong nucleophilicity, thereby can avoid the metal ion that may use in the common asymmetric catalysis.Generally should reaction use DABCO catalysis, in some reaction system, also may use the trivalent phosphine catalyst; 5), the reaction conditions gentleness, general reaction does not need anhydrous and oxygen-free as long as at room temperature stir as using DABCO catalysis, belongs to relatively close friend's reaction of reaction conditions.Therefore, theoretically, no matter in breadboard organic synthesis or in chemical industry, the Baylis-Hillman reaction all has long-range application prospect (Basavaiah, D.; Raoand, P.D.; Hyma, R.S.Tetrahedron, 1996,52,8001-8062; Basavaiah, D.; Rao, A.J.; Satyanarayana, T.Chem.Rev.2003,103,811-892).
But up to the present, Baylis-Hillman reaction application in practice is but very limited, and a major cause is for many substrates, and speed of response is too slow, and transformation efficiency is low.As for the stereoselectivity control problem of Baylis-Hillman reaction product, up to the present, effectively the method for the asymmetric Baylis-Hillman reaction of catalysis also there is not maturation, and the catalyzer that can carry out high asymmetric induction seldom.Just because of this, the Baylis-Hillman of asymmetry catalysis reaction having caused more and more chemists' interest (Iwabuchi, Y.; Nakatani, M.; Yokoyama, N.; Hatakeyama, S.J.Am.Chem.Soc.1999,121,10219-10220; Shi, M.; Xu, Y.-M.Angew.Chem.Int.Ed.2002,41,4507-4510; Shi, M.; Chen, L.-H.; Li, C.-Q.J.Am.Chem.Soc.2005,127,3790-3800; Matsui, K.; Takizawa, S.; Sasai, H.J.Am.Chem.Soc.2005,127,3680-3681).
The chiral catalyst that is used for asymmetric Baylis-Hillman reaction mainly is meant Chiral Amine and chirality phosphine two big compounds.The chiral catalyst that the success of bibliographical information is used for the Baylis-Hillman reaction of asymmetry catalysis has a common characteristic, is exactly group and a group that contains reactive hydrogen that catalyzer contains a nucleophilicity.Here the group that contains reactive hydrogen mainly is (Wang, J. such as phenolic hydroxyl group and thiocarbamide; Li, H.; Yu, X.; Zu, L.; Wang, W.Org.Lett.2005,7,4293-4296).But for chiral phosphine thiourea compound synthetic with and application in the Baylis-Hillman of asymmetry catalysis reaction also do not have bibliographical information.
Summary of the invention
The object of the invention provides a kind of chiral phosphine thiourea compound based on the dinaphthalene skeleton;
The object of the invention also provides a kind of synthetic method of above-mentioned chiral phosphine thiourea compound;
Another purpose of the present invention provides the application of a kind of above-mentioned chiral phosphine thiourea compound in the Baylis-Hillman of asymmetry catalysis reaction.
The object of the invention chiral phosphine thiourea compound has structural formula as follows
Wherein, Ar can be phenyl or R
1Or/and R
2The phenyl that replaces, described R
1Or R
2Substituting group is C
1～4Alkoxyl group, halogen, nitro or perfluor C
1～4Alkyl etc.
Typical chiral phosphine thiourea compound is that Ar is phenyl (1), rubigan (2), p-methoxyphenyl (3), p-nitrophenyl (4) or 3,5-two perfluoro-methyl phenyl (5) etc.
Chiral phosphine thiourea compound of the present invention can be with reference to known compound (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene ((R)-and 2-Amino-2 '-diphenylphosphino-1,1 '-binaphthyl) (Sumi, K.; Ikariya, T.; Noyori, R.Can.J.Chem.2000,78,697-703) single step reaction with the different sulphur nitrile of aromatic base acid esters makes.
Specifically, method of the present invention be in organic solvent and 60 ℃～reflux temperature under, (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene and molecular formula are that the reaction of the different sulphur nitrile of the aromatic base of ArNCS acid esters obtained described chiral phosphine thiourea compound in 40～150 hours, wherein, (R)-and 2-amino 2 '-diphenylphosphino-1, the mol ratio of 1 '-naphthyl naphthalene and the different sulphur nitrile of described aromatic base acid esters is 1: 1～1: 1.5, Ar can be phenyl or R
1Or and R
2The phenyl that replaces, described R
1Or R
2Substituting group is C
1～4Alkoxyl group, halogen, nitro or perfluor C
1～4Alkyl etc.Described organic solvent can be benzene,toluene,xylene, N, dinethylformamide, tetrahydrofuran (THF), 1, and 4-is to the mixed solvent of oxygen six rings, acetonitrile, dimethyl sulfoxide (DMSO), hexamethylphosphoramide or above-mentioned solvent.
Catalyzer of the present invention can be used for the Baylis-Hillman reaction shown in the catalyzed reaction formula 2, as in organic solvent and under the room temperature, adopts catalyst R of the present invention
4Base vinyl ketone and R
3The sulfimide reaction that replaces 5～100 hours, described catalyzer, R
4Base vinyl ketone and R
3The mol ratio of the sulfimide that replaces is 0.05～0.15: 1.5～2.0: 1, and reaction formula is as follows:
R wherein
3Can be C
1～12Alkyl, C
1～12Alkyl phenyl, halogenophenyl, C
1～6Alkoxyphenyl radical, nitro phenyl, benzyl or the styryl etc. that replace, R
4Can be C
1～12Alkyl, hydrogen, phenyl, C
1～6Alkoxyl group or phenoxy group.
The Baylis-Hillman reaction of catalyst methyl vinyl ketone of the present invention and sulfimide.Employing Ar is that the compound of phenyl screens as 1 pair of solvent of catalyzer, and the result is as shown in table 1:
The optimization of table 1 catalytic reaction condition
A) isolated yield.
By optimization to reaction conditions, find that methylene dichloride is best solvent, can provide 97% productive rate and 91% ee value, under this condition, other several catalyzer results obviously are not so good as catalyzer 1.
Under this reaction conditions, other several sulfimides also can obtain corresponding Baylis-Hillman product with outstanding productive rate and ee value with the methyl ethylene reactive ketone, simultaneously this catalyzer also can catalyzing propone aldehyde, the Baylis-Hillman reaction of ethyl vinyl ketone, phenyl vinyl ketone, methyl acrylate and phenyl acrylate and sulfimide, the result is as shown in table 2.The absolute configuration of product be by with relatively the drawing of known compound optically-active and HPLC spectrogram.
The expansion of table 2 substrate
A) isolated yield.
Method of the present invention is easy, and, chiral phosphine thiourea compound can be used as catalyzer in the Baylis-Hillman of asymmetry catalysis reaction, form reaction by above highly-solid selectively C-C, for the preparation of the crucial chiral intermediate in chiral drug is synthetic provides technical guarantee.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment 1
With chiral phosphine compound (R)-2-amino 2 '-diphenylphosphino-1, (453mg 1mmol) adds in the reaction tubes 1 '-naphthyl naphthalene, substitute gas, add tetrahydrofuran (THF) (2mL) behind the applying argon gas, add the different sulphur nitrile of phenyl acid esters (144 μ L again, 1.2mmol), then reaction tubes is placed 70 ℃ of oil baths.Termination reaction after 72 hours with after the methylene dichloride dilution, is transferred to reaction mixture in the flask and is spin-dried for.(eluent: ethyl acetate/petroleum ether=1/20-1/10), obtain white solid 425mg is catalyzer 1, productive rate 72% in the silica gel column chromatography separation.Ar is the catalyzer 1 of phenyl: white solid, mp.:122-124 ℃, [α]
D 20+ 193.2 (c1.00, CHCl
3) .IR (KBr): v3339,3164,3053,2924,1594,1533,1497,1433,1329,1309,1265,1238,1187,817,743,696, cm
-1.
1H NMR (300MHz, CDCl
3, TMS): δ 6.58 (2H, d, J=5.4Hz), 6.70 (1H, d, J=8.4Hz), 6.89-7.39 (18H, m), 7.50-7.56 (1H, m), 7.83 (1H, d, J=8.1Hz), 7.93 (2H, d, J=8.1Hz), 8.00 (1H, d, J=8.4Hz), 8.18 (1H, d, J=8.4Hz).
31PNMR (121.45MHz, CDCl
3, 85%H
3PO
4): δ-12.9.MS (MALDI): m/e 589 (M
++ 1) .HRMS (MALDI), C
39H
30N
2PS
+ 1: calculated value 589.1862; Measured value: 589.1880.
Embodiment 2
With chiral phosphine compound (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene (227mg, 0.5mmol) and the different sulphur nitrile of 4-chloro-phenyl-acid esters (102mg, 0.6mmol) add in the reaction tubes, substitute gas, add tetrahydrofuran (THF) (1mL) behind the applying argon gas, then reaction tubes is placed 70 ℃ of oil baths.Termination reaction after 100 hours with after the methylene dichloride dilution, is transferred to reaction mixture in the flask and is spin-dried for.(eluent: ethyl acetate/petroleum ether=1/20-1/10), obtain colorless solid 274mg, obtaining Ar is the catalyzer 2 of 4-chlorine, productive rate 88% in the silica gel column chromatography separation.Catalyzer 2: colorless solid, mp.:132-134 ℃, [α]
D 20+ 210.9 (c1.00, CHCl
3) .IR (KBr): v3351,3053,1588,1479,1392,1267,1235,1181,744,696, cm
-1.
1HNMR (300MHz, CDCl
3, TMS): δ 6.65 (2H, d, J=5.1Hz), 6.74 (1H, d, J=8.4Hz), 6.89-7.61 (19H, m), 7.83 (2H, d, J=8.1Hz), 8.03 (1H, d, J=8.1Hz), 8.22 (1H, d, J=8.1Hz).
31P NMR (121.45MHz, CDCl
3, 85%H
3PO
4): δ-13.0.MS (MALDI): m/e623 (M
++ 1) .HRMS (MALDI), C
39H
29ClN
2PS
+ 1: calculated value 623.1472; Measured value: 623.1463.
Embodiment 3
With chiral phosphine compound (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene (227mg, 0.5mmol) add in the reaction tubes, substitute gas, add tetrahydrofuran (THF) (1mL) behind the applying argon gas, (83 μ L 0.6mmol), place reaction tubes 70 ℃ of oil baths then to add the different sulphur nitrile of 4-p-methoxy-phenyl acid esters again.Termination reaction after 80 hours with after the methylene dichloride dilution, is transferred to reaction mixture in the flask and is spin-dried for.(eluent: ethyl acetate/petroleum ether=1/20-1/10), obtain colorless solid 248mg, obtaining Ar is the catalyzer 3 of 4-methoxyl group, productive rate 80% in the silica gel column chromatography separation.Catalyzer 3: white solid, mp.:128-130 ℃, [α]
D 20+ 221.9 (c1.00, CHCl
3) .IR (KBr): v3343,3051,1586,1480,1394,1267,1237,1181,747,695, cm
-1.
1H NMR (300MHz, CDCl
3, TMS): δ 3.75 (3H, s), 6.57 (2H, d, J=5.7Hz), 6.69 (1H, d, J=8.1Hz), 6.79-7.52 (19H, m), 7.80 (2H, d, J=8.1Hz), 7.97 (1H, d, J=8.1Hz), 8.13 (1H, d, J=8.1Hz).
31PNMR (121.45MHz, CDCl
3, 85%H
3PO
4): δ-13.1.MS (MALDI): m/e 619 (M
++ 1) .HRMS (MALDI), C
40H
32N
2PS
+ 1: calculated value 619.1968; Measured value: 619.1973.
Embodiment 4
With chiral phosphine compound (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene (227mg, 0.5mmol) and the different sulphur nitrile of 4-nitrophenyl acid esters (108mg, 0.6mmol) add in the reaction tubes, substitute gas, add tetrahydrofuran (THF) (1mL) behind the applying argon gas, then reaction tubes is placed 70 ℃ of oil baths.Termination reaction after 40 hours with after the methylene dichloride dilution, is transferred to reaction mixture in the flask and is spin-dried for.(eluent: ethyl acetate/petroleum ether=1/15-1/8), obtain colorless solid 247mg, obtaining Ar is the catalyzer 4 of 4-nitro, productive rate 78% in the silica gel column chromatography separation.Catalyzer 4: faint yellow solid, mp.:146-148 ℃, [α]
D 20+ 231.9 (c1.00, CHCl
3) .IR (KBr): v3361,3033,1601,1586,1481,1398,1261,1239,1181,746,697, cm
-1.
1H NMR (300MHz, CDCl
3, TMS): δ 6.69 (2H, d, J=5.1Hz), 6.79 (1H, d, J=8.4Hz), 6.91-7.59 (19H, m), 7.83 (2H, d, J=8.1Hz), 8.22 (2H, d, J=8.1Hz).
31PNMR (121.45MHz, CDCl
3, 85%H
3PO
4): δ-12.9.MS (MALDI): m/e 634 (M
++ 1) .HRMS (MALDI), C
39H
29N
3O
2PS
+ 1: calculated value 634.1713; Measured value: 634.1701.
Embodiment 5
With chiral phosphine compound (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene (113mg, 0.25mmol) add in the reaction tubes, substitute gas, add tetrahydrofuran (THF) (1mL) behind the applying argon gas, add 3 again, the different sulphur nitrile of 5-two trifluoromethyls acid esters (55 μ L, 0.3mmol), then reaction tubes is placed 70 ℃ of oil baths.Termination reaction after 150 hours with after the methylene dichloride dilution, is transferred to reaction mixture in the flask and is spin-dried for.(eluent: ethyl acetate/petroleum ether=1/20-1/10), obtain colorless solid 170mg, obtaining Ar is the catalyzer 5 of 4-nitrophenyl, productive rate 94% in the silica gel column chromatography separation.Catalyzer 5: colorless solid, mp.:90-92 ℃, [α]
D 20+ 363.9 (c1.00, CHCl
3) .IR (KBr): v3358,3053,1534,1478,1382,1278,1252,1178,1133,742,696, cm
-1.
1H NMR (300MHz, CDCl
3, TMS): δ 6.74 (1H, d, J=8.1Hz), 6.97-7.30 (13H, m), 7.38 (1H, d, J=3.9Hz, NH), 7.39-7.56 (4H, m), 7.62 (2H, s), 7.67 (1H, d, J=8.1Hz), 7.90-7.95 (3H, m), 8.08 (1H, d, J=8.4Hz), 8.22 (1H, d, J=3.9Hz, NH).
31P NMR (121.45MHz, CDCl
3, 85%H
3PO
4): δ-12.9.MS (ESI): m/e725 (M
++ 1) .HRMS (ESI), C
41H
28N
2F
6PS
+ 1: calculated value 725.1609; Measured value: 725.1617.
Embodiment 6
The sulfimide of adding phenyl aldehyde in reaction tubes (65mg, 0.25mmol), catalyzer 1 (15mg, 0.025mmol), fill as argon gas after substituting gas, in system, add methylene dichloride 1mL, (42 μ L, 0.5mmol), stirring at room is stopped reaction after 10 hours to add methyl vinyl ketone then.Reaction mixture with after the methylene dichloride dilution, is transferred in the flask and is spin-dried for.Silica gel column chromatography separates (eluent: ethyl acetate/petroleum ether=1/5), obtain white solid 80mg, productive rate 97%.Compound data: a white solid, mp:106-110 ℃ of .[α]
D 20+ 35.3 (c1.0, CHCl
3).
1H NMR (CDCl
3, TMS, 300MHz): δ 2.16 (3H, s, Me), 2.42 (3H, s, Me), 5.26 (1H, d, J=8.6Hz), 5.61 (1H, d, J=8.6Hz), 6.10 (1H, s), 6.11 (1H, s), 7.11 (2H, m, Ar), and 7.20-7.27 (5H, m, Ar), 7.66 (2H, d, J=8.1Hz, Ar). these hydrogen spectrum data consistent (Shi, M. with given data; Xu, Y.-M.Angew.Chem.Int.Ed.2002,41,4507-4510).The HPLC:AD post; λ=254nm; Drip washing: hexane/isopropyl alcohol=80/20; Flow velocity: 0.7mL/min; t
Major=11.5min, t
Minor=13.0min; Ee%=91%.
Embodiment 7
The sulfimide of adding phenyl aldehyde in reaction tubes (65mg, 0.25mmol), catalyzer 1 (15mg, 0.025mmol), fill as argon gas after substituting gas, in system, add methylene dichloride 1mL, (44 μ L, 0.5mmol), stirring at room is stopped reaction after 30 hours to add methyl methacrylate then.Reaction mixture with after the methylene dichloride dilution, is transferred in the flask and is spin-dried for.Silica gel column chromatography separates (eluent: ethyl acetate/petroleum ether=1/5), obtain white solid 61mg, productive rate 71%.Compound data: a white solid, mp:71-75 ℃ of .[α]
D 20+ 17.2 (c1.00, CHCl
3).
1H NMR (CDCl
3, TMS, 300MHz): δ 2.41 (3H, s, Me), 3.61 (3H, s, Me), 5.25 (1H, d, J=9.1Hz, NH), 5.72 (1H, d, J=9.1Hz), 5.79 (1H, s), 6.20 (1H, s), 7.09 (2H, d, J=8.6Hz, Ar), 7.20 (2H, d, J=8.6Hz, Ar), 7.23 (2H, d, J=8.3Hz, Ar), 7.65 (2H, d, J=8.3Hz, Ar). these hydrogen spectrum data consistent (Shi, M. with given data; Xu, Y.-M.; Shi, Y.-L.Chem.Eur.J.2005,11,1794-1802).The HPLC:AD post; λ=254nm; Drip washing: hexane/isopropyl alcohol=80/20; Flow velocity: 0.7mL/min; t
Major=10.6min, t
Minor=12.3min; Ee%=77%.
Claims (4)
1. chiral phosphine thiourea compound, it has following structural formula
Wherein, Ar is phenyl or R
1Or/and R
2The phenyl that replaces, described R
1Or R
2Substituting group is C
1～4Alkoxyl group, halogen, nitro or perfluor C
1～4Alkyl.
2. the synthetic method of a chiral phosphine thiourea compound as claimed in claim 1, it is characterized in that in organic solvent and 60 ℃～reflux temperature under, (R)-2-amino 2 '-diphenylphosphino-1,1 '-naphthyl naphthalene and molecular formula are that the different sulphur nitrile acid esters of ArNCS reacted 40～150 hours, (R)-2-amino 2 '-diphenylphosphino-1, the mol ratio of 1 '-naphthyl naphthalene and the different sulphur nitrile of described aromatic base acid esters is 1: 1～1: 1.5, and Ar according to claim 1.
3. the application of a chiral phosphine thiourea compound as claimed in claim 1 is characterized in that this compound is used for the catalyzer of the asymmetric catalysis of Baylis-Hillman.
4. the application of chiral phosphine thiourea compound as claimed in claim 3 is characterized in that the compound of the structural formula that described asymmetric catalysis is used to be prepared as follows:
Wherein, R
3Be C
1～12Alkyl, C
1～12Alkyl phenyl, halogenophenyl, C
1～6Alkoxyphenyl radical, the nitro phenyl, benzyl or the styryl that replace; R
4Be C
1～12Alkyl, hydrogen, phenyl, C
1～6Alkoxyl group or phenoxy group.
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| CN109053800B (en) * | 2018-07-30 | 2020-08-14 | 湖北大学 | Quaternary phosphonium salt supported chiral amino-thiourea and preparation method and application thereof |
| CN113117744A (en) * | 2021-04-08 | 2021-07-16 | 天津大学 | Chiral sugar-containing thiosemicarbazide catalyst derived from binaphthalene skeleton and preparation method and application thereof |
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