CN101486737B - Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction - Google Patents
Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction Download PDFInfo
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- CN101486737B CN101486737B CN2009100087409A CN200910008740A CN101486737B CN 101486737 B CN101486737 B CN 101486737B CN 2009100087409 A CN2009100087409 A CN 2009100087409A CN 200910008740 A CN200910008740 A CN 200910008740A CN 101486737 B CN101486737 B CN 101486737B
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- UUHMWERABBLRBQ-UHFFFAOYSA-N CC1C=C=CCC1 Chemical compound CC1C=C=CCC1 UUHMWERABBLRBQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a ferrocene phosphinimine ligand containing a quaternary ammonium salt group, a preparation method thereof and an application thereof in catalyzing an asymmetric allyl substitution reaction. The preparation method thereof is as follows: 1-(2-Diphenylphosphine) ferrocene ethylamine and aromatic aldehyde quaternary ammonium salt are dissolved in dichloromethane to obtain a solution; a dehydrating agent is added to the solution and stirred at room temperature to obtain a product; and the product is washed with an organic solvent and the compound of the invention is obtained after the product is dried. The catalysis of an asymmetric allyl substitution reaction by the compound comprises the following steps: an allyl palladium chloride dipolymer and a chiral ligand are dissolved in dichloromethane to obtain a solution; the solution reacts under argon shield at room temperature; 1,3-diphenyl-2-allyl-1-acetic acid ester of alcohol, methylmalonate, N,O-bis (trimethylsilyl) acetamide and anhydrous potassium acetate are added to the solution in sequence; and the solution is sealed to react; and then a substitution is obtained through extraction, drying, concentration and purification. The compound is characterized by simple synthesis line, simple operation, being easy to purify, high production rate, good catalytic activity and high thermal stability.
Description
Technical field
The invention belongs to the asymmetric synthesis technical field, relate to a kind of ferrocene phosphinimine ligand, its preparation and application aspect catalysis that contains the quaternary amine group.
Technical background
Ferrocene-containing compound obtains significant progress with its its specific structure character in fields such as electrochemistry, materialogy, nonlinear opticses.From stereochemical viewpoint, one of most important character of ferrocene-containing compound is exactly when having plural different substituents on the same luxuriant ring of ferrocene, will produce planar chiral.Just because of the space structure of ferrocene uniqueness and the characteristics of derivatize easily, make a large amount of planar chiral ferrocene derivatives be used for various asymmetric catalysis as the chiral ligand of excellence.Wherein, ferrocene phosphinimine ligand has extraordinary catalytic effect in asymmetric allyl substitution reaction, asymmetric hydrogen transfer reactions.But ferrocene-containing compound is soluble in most organic solvents, is difficult to extraction separation after the catalyzed reaction, has caused the chiral ligand of a large amount of costlinesses to be difficult to recycle, and has hindered the application of ferrocene analog derivative in the industrialization asymmetry catalysis greatly.The method that reclaims at present the ferrocene catalyzer has a lot, one of the most frequently used method be the ferrocene catalyzer by immobilized on different carriers, as superpolymer, silica gel, dendritic polymer, MCM-41 etc.But above-mentioned several class methods have reduced the solvability of catalyzer, influence catalytic effect.
The chiral ferrocene phosphinimine that contains the quaternary amine group is the novel part of a class, because this series part contains the quaternary amine group, therefore should series not only have special coordination ability, and have special solvability.Because this series part contains ferrocene group, so it is at methylene dichloride, N, has good solvability in the organic solvent such as dinethylformamide, dimethyl sulfoxide (DMSO), again because it contains the quaternary amine group, so conventional organic solvents such as its almost insoluble and ether, normal hexane, ethyl acetate.Its solvability is carried out deep research, and this series part just has the prospect that realizes recyclable utilization, has important industry and learning value.
Summary of the invention
The objective of the invention is in order to develop a kind of novel ferrocene phosphinimine ligand, and provide a kind of catalytic efficiency the high ferrocene phosphinimine ligand that contains the quaternary amine group.
Further aim of the present invention provides the above-mentioned preparation method who contains the ferrocene phosphinimine ligand of quaternary amine group.
Another object of the present invention is to contain the ferrocene phosphinimine ligand of quaternary amine group as efficient, the application of green catalyst in asymmetric allyl substitution reaction.
The objective of the invention is to be achieved through the following technical solutions.
The ferrocene phosphinimine ligand that a class of the present invention contains the quaternary amine group is the compound of following general formula:
Wherein the chirality of ferrocene frame having ferrocene frame be respectively (R, Sp), (S, Rp).
The ferrocene phosphinimine ligand synthetic method that contains the quaternary amine group of the present invention need be with 4-aldehyde radical-N, N, and N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt is a starting raw material, its synthetic method has following several:
Method one, with 4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine or 3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine is dissolved in the distilled water, drip the aqueous solution of the phosphorus hexafluoride acid ammonium of equimolar amount, react 2～5 hours under the room temperature after, filter and obtain the aromatic aldehyde quaternary amine that negatively charged ion is the phosphorus hexafluoride acid group.
The general formula of described reaction is:
Method two, with 4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine or 3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine is dissolved in the distilled water, drips the silver acetate of equimolar amount or the aqueous solution of trifluoroacetic acid silver, react 2～5 hours under the room temperature after, filter, will obtain the aromatic aldehyde quaternary amine that negatively charged ion is acetate or trifluoroacetic acid root after the filtrate drying.
The general formula of described reaction is:
Method three, 4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine or 3-aldehyde radical-N, N, the ammonium tetrafluoroborate of N-trimethylaniline salt compounded of iodine and equimolar amount joins in the ethyl acetate, after reacting 1～8 hour under the room temperature, filter, will obtain the aromatic aldehyde quaternary amine that negatively charged ion is a tetrafluoride roc acid group after the filtrate drying.
The general formula of described reaction is:
Method four, with 4-aldehyde radical-N, accelerine or 4-aldehyde radical-N, accelerine is dissolved in the ethyl acetate, adds the trifluoromethanesulfonic acid methyl esters of equimolar amount, room temperature reaction 12～18 hours obtains the aromatic aldehyde quaternary amine that negatively charged ion is the trifluoromethanesulfonic acid root after filtration, the drying.
The general formula of described reaction is:
The ferrocene phosphinimine ligand that contains the quaternary amine group of the present invention synthesizes by the following method:
With 4-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt, 1-(2-diphenylphosphine) ferrocene ethamine are dissolved in the methylene dichloride, add dewatering agent, stirred under the room temperature 1～8 hour, dewatering agent is filtered, mother liquor concentrates and obtains yellow solid, use organic solvent washing, obtain containing the ferrocene phosphinimine ligand of quaternary amine group after the drying, its general formula is as follows:
Wherein the chirality of ferrocene frame having ferrocene frame be respectively (R, Sp), (S, Rp); R is the aromatic group that contains quaternary amine.
The general formula of described reaction is:
Described 4-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, the amount ratio of N-trimethylaniline quaternary ammonium salt and 1-(2-diphenylphosphine) ferrocene ethamine is 1: 1.01～1.10 (mol ratios); Described dewatering agent comprise anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous,
Molecular sieve; Described organic solvent comprises anhydrous diethyl ether, ethyl acetate, normal hexane, sherwood oil, benzene, toluene; Described solvent load is every mmole 4-aldehyde radical-N, N, and N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt uses 1～5ml methylene dichloride.
The catalytic applications of ferrocene phosphinimine ligand in asymmetric allyl substitution reaction that contains the quaternary amine group of the present invention, concrete steps are as follows:
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2Be dissolved in the methylene dichloride with the ferrocene phosphinimine ligand that contains the quaternary amine group; room temperature reaction is 0～2 hour under the argon shield; in this solution, add 1 successively; 3-phenylbenzene-2-allyl group-the acetic ester of 1-alcohol, dimethyl malonate, N; O-two (trimethyl silicane) ethanamide (BSA) and Glacial acetic acid potassium, confined reaction 12～48 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, purifying obtains replacing product.Described reaction formula is:
The described consumption that contains the ferrocene phosphinimine ligand of quaternary amine group is allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
22～3 times (mol ratios); The described consumption that contains the ferrocene phosphinimine ligand of quaternary amine group is 1,1%～5% (molecular fraction) of the acetic ester of 3-phenylbenzene-2-allyl group-1-alcohol; Described 1, the 3-phenylbenzene-2-allyl group-acetic ester of 1-alcohol, dimethyl malonate, N, the mol ratio of O-two (trimethyl silicane) ethanamide (BSA) and Glacial acetic acid potassium is 1: 2～4: 2～4: 0.01～0.02; Described solvent load is every mmole 1, and the acetic ester of 3-phenylbenzene-2-allyl group-1-alcohol uses 8～10ml methylene dichloride.
Beneficial effect
The ferrocene phosphinimine ligand that contains the quaternary amine group of the present invention has the advantages that synthetic line is simple, simple to operate, to be easy to purifying, productive rate height, catalytic activity good, and thermostability is high.
Embodiment
Further describe the present invention below in conjunction with embodiment:
Embodiment 1:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline salt compounded of iodine synthetic
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (291mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 5h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 91%.m.p.＝145～146℃。[α]
D 25＝-324.15(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.524(d，3H，J＝6.6Hz，CHCH
3)，3.456(s，9H，CH
3)，4.401(s，5H，unsubstrated?Cp-H)，3.361-4.719(m，3H，substrated?Cp-H)，4.722(m，1H，CHMe)，6.875～7.878(m，14H，Ph-H)，8.124(s，1H，N＝CH)。MALDIm：z＝559.4，M
+。Anal.Calc.for?C34H36FeIN2P：C，59.49；H，5.29；N，4.08.Found：C，59.74；H，5.21；N，3.91.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline salt compounded of iodine, raw material is changed into (S, R
p)-PPFNH
2, productive rate 93%.[α]
D 25＝+325.60(c＝0.6，CH
2Cl
2)。
Embodiment 2:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline hexafluorophosphate synthetic
4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) be dissolved in the 10ml distilled water, drip ammonium hexafluorophosphate (984mg, 6mmol) aqueous solution, room temperature reaction 4h, the adularescent solid is separated out, and filters distilled water thorough washing solid, vacuum-drying, obtain 4-aldehyde radical-N, N, N-trimethylaniline hexafluorophosphate.Productive rate 89%.m.p.＝170～171℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ3.669(s，9H，CH
3)，8.155～8.239(m，4H，Ph-H)，10.124(s，1H，CHO)。ESI：m：z＝164M
+，m：z＝145M
-。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 4-aldehyde radical-N, N, N-trimethylaniline hexafluorophosphate (309mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 5h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 92%.m.p.＝205～206℃。[α]
D 25＝-364.75(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.548(d，3H，J＝6.6Hz，CHCH
3)，3.546(s，9H，CH
3)，4.044(s，5H，unsubstrated?Cp-H)，3.666-4.659(m，3H，substratedCp-H)，4.802(m，1H，CHMe)，6.835～7.748(m，14H，Ph-H)，8.104(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+，ESI，m：z＝145M
-。Anal.Calc.for?C34H36F6FeN2P2：C，57.97；H，5.15；N，3.98.Found：C，57.94；H，5.21；N，3.91.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline hexafluorophosphate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 93%.[α]
D 25＝+362.60(c＝0.6，CH
2Cl
2)。
Embodiment 3:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline a tetrafluoro borate synthetic
4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) and ammonium tetrafluoroborate (524.2mg, 5mmol) join in the 10ml ethyl acetate, room temperature reaction 4h, the adularescent solid is separated out, filter, the filtrate evaporate to dryness, vacuum-drying obtains 4-aldehyde radical-N, N, N-trimethylaniline tetrafluoride borate.Productive rate 78%.m.p.＝110～111℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ3.669(s，9H，CH
3)，8.155～8.239(m，4H，Ph-H)，10.124(s，1H，CHO)。ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 4-aldehyde radical-N, N, N-trimethylaniline a tetrafluoro borate (251mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 8h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 89%.m.p.＝162～166℃。[α]
D 25＝-334.51(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substratedCp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C34H36BF4FeN2P：C，63.19；H，5.61；N，4.33.Found：C，62.96；H，5.36；N，4.61.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline a tetrafluoro borate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 87%.[α]
D 25＝+332.56(c＝0.6，CH
2Cl
2)。
Embodiment 4:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-phenylglycine salt synthetic
4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) and silver acetate (834.5mg 5mmol) joins in the 200ml distilled water, room temperature reaction 2h has brown solid to separate out, and filters the filtrate evaporate to dryness, vacuum-drying obtains 4-aldehyde radical-N, N, N-trimethylaniline acetate.Productive rate 97%.m.p.＝172～173℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ2.238(s，3H，COCH
3)，3.869(s，9H，CH
3)，8.255～8.393(m，4H，Ph-H)，10.125(s，1H，CHO)。ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 4-aldehyde radical-N, N, N-trimethylaniline acetate (223mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 6h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 93%.m.p.＝216～218℃。[α]
D 25＝-351.21(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，2.238(s，3H，COCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substrated?Cp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C36H39FeN2O2P：C，69.91；H，6.36；N，4.53.Found：C，69.66；H，6.66；N，4.61.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for phenylglycine salt, raw material is changed into (S, R
p)-PPFNH
2, productive rate 96%.[α]
D 25＝+352.56(c＝0.6，CH
2Cl
2)。
Embodiment 5:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline trifluoroacetate synthetic
4-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) (1.104g 5mmol) joins in the 200ml distilled water with trifluoroacetic acid silver, room temperature reaction 2h has brown solid to separate out, and filters the filtrate evaporate to dryness, vacuum-drying obtains 4-aldehyde radical-N, N, N-trimethylaniline trifluoroacetate.Productive rate 97%.m.p.＝159～160℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ3.869(s，9H，CH
3)，8.255～8.393(m，4H，Ph-H)，10.125(s，1H，CHO)。ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 4-aldehyde radical-N, N, N-trimethylaniline trifluoroacetate (277mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 5h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 93%.m.p.＝187～188℃。[α]
D 25＝-347.21(c＝0.6，?CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substratedCp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C36H36F3FeN2O2P：C，64.30；H，5.40；N，4.17.Found：C，64.76；H，5.66；N，4.41.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline trifluoroacetate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 96%.[α]
D 25＝+345.56(c＝0.6，CH
2Cl
2)。
Embodiment 6:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline fluoroform sulphonate synthetic
4-aldehyde radical-N, and accelerine (746mg, 5mmol) (985mg 6mmol) is dissolved in the 10ml methylene dichloride with the trifluoromethanesulfonic acid methyl esters, room temperature reaction spends the night, and adds anhydrous diethyl ether, has precipitation to separate out, and filters, filter cake washs with ether, product vacuum-drying, productive rate 67%
1H-NMR (300MHz, DMSO
4-d
6): δ 3.63 (s, 9H, NMe
3), 8.12-8.22 (m, 4H, Ph-H), 10.11 (1H, s, CHO).ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 4-aldehyde radical-N, N, N-trimethylaniline fluoroform sulphonate (298mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 6h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 95%.m.p.＝132～133℃。[α]
D 25＝-362.61(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substratedCp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C35H36F3FeN2O3PS：C，59.33；H，5.12；N，3.95.Found：C，59.76；H，5.36；N，4.01.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline fluoroform sulphonate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 96%.[α]
D 25＝+365.56(c＝0.6，CH
2Cl
2)。
Embodiment 7:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline salt compounded of iodine synthetic
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (291mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 5h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 91%.m.p.＝125～126℃。[α]
D 25＝-314.15(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.524(d，3H，J＝6.6Hz，CHCH
3)，3.456(s，9H，CH
3)，4.401(s，5H，unsubstrated?Cp-H)，3.361-4.719(m，3H，substrated?Cp-H)，4.722(m，1H，CHMe)，6.875～7.878(m，14H，Ph-H)，8.124(s，1H，N＝CH)。MALDIm：z＝559.4，M
+。Anal.Calc.for?C34H36FeIN2P：C，59.49；H，5.29；N，4.08.Found：C，59.74；H，5.21；N，3.91.
N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline salt compounded of iodine, raw material is changed into (S, R
p)-PPFNH
2, productive rate 93%.[α]
D 25＝+315.60(c＝0.6，CH
2Cl
2)。
Embodiment 8:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline hexafluorophosphate synthetic
3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) be dissolved in the 10ml distilled water, drip ammonium hexafluorophosphate (984mg, 6mmol) aqueous solution, room temperature reaction 4h, the adularescent solid is separated out, and filters distilled water thorough washing solid, vacuum-drying, obtain 3-aldehyde radical-N, N, N-trimethylaniline hexafluorophosphate.Productive rate 89%.m.p.＝170～171℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ3.669(s，9H，CH
3)，8.155～8.239(m，4H，Ph-H)，10.124(s，1H，CHO)。ESI：m：z＝164M
+，m：z＝145M
-。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 3-aldehyde radical-N, N, N-trimethylaniline hexafluorophosphate (309mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 5h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 92%.m.p.＝185～186℃。[α]
D 25＝-354.75(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.548(d，3H，J＝6.6Hz，CHCH
3)，3.546(s，9H，CH
3)，4.044(s，5H，unsubstrated?Cp-H)，3.666-4.659(m，3H，substratedCp-H)，4.802(m，1H，CHMe)，6.835～7.748(m，14H，Ph-H)，8.104(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+，ESI，m：z＝145M
-。Anal.Calc.for?C34H36F6FeN2P2：C，?57.97；H，5.15；N，3.98.Found：C，57.94；H，5.21；N，3.91.
N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline hexafluorophosphate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 93%.[α]
D 25＝+352.60(c＝0.6，CH
2Cl
2)。
Embodiment 9:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline a tetrafluoro borate synthetic
3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) and ammonium tetrafluoroborate (524.2mg, 5mmol) join in the 10ml ethyl acetate, room temperature reaction 4h, the adularescent solid is separated out, filter, the filtrate evaporate to dryness, vacuum-drying obtains 3-aldehyde radical-N, N, N-trimethylaniline tetrafluoride borate.Productive rate 78%.m.p.＝110～111℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ3.669(s，9H，CH
3)，8.155～8.239(m，4H，Ph-H)，10.124(s，1H，CHO)。ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 3-aldehyde radical-N, N, N-trimethylaniline a tetrafluoro borate (251mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 8h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 89%.m.p.＝152～156℃。[α]
D 25＝-324.51(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substratedCp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C34H36BF4FeN2P：C，63.19；H，5.61；N，4.33.Found：C，62.96；H，5.36；N，4.61.
N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline a tetrafluoro borate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 87%.[α]
D 25＝+332.56(c＝0.6，CH
2Cl
2)。
Embodiment 10:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-phenylglycine salt synthetic
3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) and silver acetate (834.5mg 5mmol) joins in the 200ml distilled water, room temperature reaction 2h has brown solid to separate out, and filters the filtrate evaporate to dryness, vacuum-drying obtains 3-aldehyde radical-N, N, N-trimethylaniline acetate.Productive rate 97%.m.p.＝172～173℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ2.238(s，3H，COCH
3)，3.869(s，9H，CH
3)，?8.255～8.393(m，4H，Ph-H)，10.125(s，1H，CHO)。ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 3-aldehyde radical-N, N, N-trimethylaniline acetate (223mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 6h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 93%.m.p.＝206～208℃。[α]
D 25＝-341.21(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，2.238(s，3H，COCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substrated?Cp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C36H39FeN2O2P：C，69.91；H，6.36；N，4.53.Found：C，69.66；H，6.66；N，4.61.
N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for phenylglycine salt, raw material is changed into (S, R
p)-PPFNH
2, productive rate 96%.[α]
D 25＝+342.56(c＝0.6，CH
2Cl
2)。
Embodiment 11:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline trifluoroacetate synthetic
3-aldehyde radical-N, N, N-trimethylaniline salt compounded of iodine (1.455g, 5mmol) (1.104g 5mmol) joins in the 200ml distilled water with trifluoroacetic acid silver, room temperature reaction 2h has brown solid to separate out, and filters the filtrate evaporate to dryness, vacuum-drying obtains 3-aldehyde radical-N, N, N-trimethylaniline trifluoroacetate.Productive rate 97%.m.p.＝159～160℃。
1H-NMR(300MHz，DMSO
4-d
6)：δ3.869(s，9H，CH
3)，8.255～8.393(m，4H，Ph-H)，10.125(s，1H，CHO)。ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 3-aldehyde radical-N, N, N-trimethylaniline trifluoroacetate (277mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 5h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 93%.m.p.＝177～178℃。[α]
D 25＝-337.21(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substratedCp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C36H36F3FeN2O2P：C，64.30；H，5.40；N，4.17.Found：C，64.76；H，5.66；N，4.41.
N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline trifluoroacetate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 96%.[α]
D 25＝+335.56(c＝0.6，CH
2Cl
2)。
Embodiment 12:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline fluoroform sulphonate synthetic
3-aldehyde radical-N, and accelerine (746mg, 5mmol) (985mg 6mmol) is dissolved in the 10ml methylene dichloride with the trifluoromethanesulfonic acid methyl esters, room temperature reaction spends the night, and adds anhydrous diethyl ether, has precipitation to separate out, and filters, filter cake washs with ether, product vacuum-drying, productive rate 67%
1H-NMR (300MHz, DMSO
4-d
6): δ 3.63 (s, 9H, NMe
3), 8.12-8.22 (m, 4H, Ph-H), 10.11 (1H, s, CHO).ESI：m：z＝164M
+。
(R, S
p)-PPFNH
2(433mg, 1.05mmol), 3-aldehyde radical-N, N, N-trimethylaniline fluoroform sulphonate (298mg, 1mmol) and the 500mg anhydrous sodium sulphate be positioned in the 10ml Xiu Langke bottle, add the anhydrous CH of 3ml
2Cl
2, stirring at room 6h filters, and revolves to steam to remove organic solvent and obtain yellow solid, and product obtains product with the anhydrous diethyl ether washing.Productive rate 95%.m.p.＝122～123℃。[α]
D 25＝-332.61(c＝0.6，CH
2Cl
2)。
1H-NMR(300MHz，DMSO
4-d
6)：δ1.249(d，3H，J＝6.6Hz，CHCH
3)，3.375(s，9H，CH
3)，4.124(s，5H，unsubstrated?Cp-H)，3.326-4.374(m，3H，substratedCp-H)，4.793(m，1H，CHMe)，6.785～7.639(m，14H，Ph-H)，8.216(s，1H，N＝CH)。MALDI?m：z＝559.4，M
+。Anal.Calc.for?C35H36F3FeN2O3PS：C，59.33；H，5.12；N，3.95.Found：C，59.76；H，5.36；N，4.01.
N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-preparation method is the same for the aniline fluoroform sulphonate, raw material is changed into (S, R
p)-PPFNH
2, productive rate 96%.[α]
D 25＝+335.56(c＝0.6，CH
2Cl
2)。
Embodiment 13:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline salt compounded of iodine
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and part N; N; N-trimethylammonium-4-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline salt compounded of iodine (17.2mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 95%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 88.5%.
With N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline salt compounded of iodine, yield: 90%, the product absolute configuration is S, the ee value is 60.5%.
Embodiment 14:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline hexafluorophosphate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-4-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline hexafluorophosphate (17.6mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 93%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 86.5%.
With N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline hexafluorophosphate, yield: 95%, the product absolute configuration is S, the ee value is 78.5%.
Embodiment 15:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline a tetrafluoro borate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-4-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline a tetrafluoro borate (16.2mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 91%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 90.5%.
With N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline a tetrafluoro borate, yield: 95%, the product absolute configuration is S, the ee value is 79.5%.
Embodiment 16:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of phenylglycine salt
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-4-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-phenylglycine salt (15.5mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 92%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 92.5%.
With N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of phenylglycine salt, yield: 95%, the product absolute configuration is S, the ee value is 80.5%.
Embodiment 17:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline trifluoroacetate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-4-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline trifluoroacetate (16.8mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 92%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 94.5%.
With N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline trifluoroacetate, yield: 95%, the product absolute configuration is S, the ee value is 80.5%.
Embodiment 18:N, N, N-trimethylammonium-4-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline fluoroform sulphonate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-4-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline fluoroform sulphonate (17.7mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 92%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 89.5%.
With N, N, N-trimethylammonium-4-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline fluoroform sulphonate, yield: 92%, the product absolute configuration is S, the ee value is 70.5%.
Embodiment 19:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline salt compounded of iodine
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-3-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline salt compounded of iodine (17.2mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 95%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 91.5%.
With N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline salt compounded of iodine, yield: 90%, the product absolute configuration is S, the ee value is 64.5%.
Embodiment 20:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline hexafluorophosphate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-3-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline hexafluorophosphate (17.6mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 93%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 88.5%.
With N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline hexafluorophosphate, yield: 95%, the product absolute configuration is S, the ee value is 80.5%.
Embodiment 21:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline a tetrafluoro borate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-3-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline a tetrafluoro borate (16.2mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 92%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 93.5%.
With N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline a tetrafluoro borate, yield: 95%, the product absolute configuration is S, the ee value is 82.5%.
Embodiment 22:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of phenylglycine salt
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-3-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-phenylglycine salt (15.5mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 95%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 94.5%.
With N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of phenylglycine salt, yield: 95%, the product absolute configuration is S, the ee value is 82.5%.
Embodiment 23:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline trifluoroacetate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-3-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline trifluoroacetate (16.8mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 94%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 95.5%.
With N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline trifluoroacetate, yield: 95%, the product absolute configuration is S, the ee value is 82.5%.
Embodiment 24:N, N, N-trimethylammonium-3-[[1-[2-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-the catalytic asymmetric allyl substitution reaction of aniline fluoroform sulphonate
With allyl palladium chloride dimer [Pd (Cl of η-C3H5)]
2(3.7mg; 0.010mmol) and chiral ligand N; N; N-trimethylammonium-3-[[1 (R)-[2 (S)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-aniline fluoroform sulphonate (17.7mg; 0.025mmol) be dissolved in the 1ml methylene dichloride; room temperature reaction is 1 hour under the argon shield; in this solution, add 1 successively; acetic ester (the 126mg of 3-phenylbenzene-2-allyl group-1-alcohol; 0.5mmol); dimethyl malonate (170 μ l, 1.5mmol); N, O-two (trimethyl silicane) ethanamide (BSA) (370 μ l; 1.5mmol) and Glacial acetic acid potassium 1.0mg, confined reaction 24 hours.Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, (eluent: sherwood oil: ethyl acetate=20: 1), purifying obtains replacing product to column chromatography for separation.Yield: 91%, HPLC analysed preparation enantiomer excessive value (ee value) (Chiralpak AD-H, normal hexane: Virahol=90: 10,1.0ml/min), the product absolute configuration is R, the ee value is 91.5%.
With N, N, N-trimethylammonium-3-[[1 (S)-[2 (R)-(diphenylphosphino) ferrocenyl]-ethyl-imines]-methyl]-during the catalysis of aniline fluoroform sulphonate, yield: 92%, the product absolute configuration is S, the ee value is 72.5%.
Claims (5)
1. ferrocene phosphinimine ligand that contains the quaternary amine group is characterized in that the compound general formula is:
Wherein the chirality of ferrocene frame having ferrocene frame be respectively (R, Sp), (S, Rp).
2. a kind of preparation method who contains the ferrocene phosphinimine ligand of quaternary amine group as claimed in claim 1, it is characterized in that: with 4-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt, 1-(2-diphenylphosphine) ferrocene ethamine are dissolved in the methylene dichloride, add dewatering agent, stirred under the room temperature 1～8 hour, dewatering agent is filtered, mother liquor concentrates and obtains yellow solid, uses organic solvent washing, obtains containing the ferrocene phosphinimine ligand of quaternary amine group after the drying.
3. a kind of preparation method who contains the ferrocene phosphinimine ligand of quaternary amine group as claimed in claim 2, it is characterized in that: described 4-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, the mol ratio of N-trimethylaniline quaternary ammonium salt and 1-(2-diphenylphosphine) ferrocene ethamine is 1: 1.01～1.10; Described dewatering agent be anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous or
Molecular sieve; Described organic solvent is anhydrous diethyl ether, ethyl acetate, normal hexane, sherwood oil, benzene or toluene; Described solvent load is every mmole 4-aldehyde radical-N, N, and N-trimethylaniline quaternary ammonium salt or 3-aldehyde radical-N, N, N-trimethylaniline quaternary ammonium salt uses 1～5m1 methylene dichloride.
4. a kind of application that contains the ferrocene phosphinimine ligand of quaternary amine group at asymmetric allyl substitution reaction as claimed in claim 1 is characterized in that: with allyl palladium chloride dimer [Pd (C1 of η-C3H5)]
2Be dissolved in the methylene dichloride with the ferrocene phosphinimine ligand that contains the quaternary amine group, room temperature reaction is 0～2 hour under the argon shield, in this solution, add 1 successively, 3-phenylbenzene-2-allyl group-the acetic ester of 1-alcohol, dimethyl malonate, N, O-two (trimethyl silicane) ethanamide (BSA) and Glacial acetic acid potassium, confined reaction 12～48 hours; Add saturated ammonium chloride solution and finish reaction, extraction, dry, concentrate, purifying obtains replacing product.
5. a kind of application that contains the ferrocene phosphinimine ligand of quaternary amine group at asymmetric allyl substitution reaction as claimed in claim 4 is characterized in that: described ferrocene phosphinimine ligand that contains the quaternary amine group and allyl palladium chloride dimer [Pd (C1 of η-C3H5)]
2Mol ratio be 2～3: 1; The described ferrocene phosphinimine ligand and 1 that contains the quaternary amine group, the mol ratio of the acetic ester of 3-phenylbenzene-2-allyl group-1-alcohol is 0.01～0.05: 1; Described 1, the 3-phenylbenzene-2-allyl group-acetic ester of 1-alcohol, dimethyl malonate, N, the mol ratio of O-two (trimethyl silicane) ethanamide and Glacial acetic acid potassium is 1: 2～4: 2～4: 0.01～0.02; Described solvent load is every mmole 1, and the acetic ester of 3-phenylbenzene-2-allyl group-1-alcohol uses 8～10ml methylene dichloride.
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