CN101565436A - 3, 3'-position biaryl group binaphthyl shaft chiral phosphoramidite ligand and preparation method thereof - Google Patents
3, 3'-position biaryl group binaphthyl shaft chiral phosphoramidite ligand and preparation method thereof Download PDFInfo
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- CN101565436A CN101565436A CNA2009100691935A CN200910069193A CN101565436A CN 101565436 A CN101565436 A CN 101565436A CN A2009100691935 A CNA2009100691935 A CN A2009100691935A CN 200910069193 A CN200910069193 A CN 200910069193A CN 101565436 A CN101565436 A CN 101565436A
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Abstract
The invention relates to a 3, 3'-position binaphthyl shaft chiral phosphoramidite ligand containing biaryl group and a preparation method thereof. The preparation method comprises the following steps of: leading 3, 3'-dual-biaryl group-2, 2'-dinaphthol to react with hexagon-alkyl group phosphoramidite in organic solvent at the temperature of 0-120 DEG C according to the mol rate of 1:1, or leading 3, 3'- dual-biaryl group-2, 2'-dinaphthol to react with phosphorus trichloride and dialkyl amine in steps, and after complete reaction, the object chiral phosphoramidite ligand can be obtained through washing, extraction and separation. After going through complexation with metallic copper salt, the chiral phosphoramidite ligand can be used for catalyzing the conjugate addition reaction of zinc alkyl with alpha, beta-unsaturated carbonyl compounds, and an additional product is prepared with high yield up to 78-98% and high enantioselectivity ee value up to 80-98%.
Description
Technical field
The present invention relates to a class novel chiral phosphoramidite ligand, is to disclose a class to contain 33 '-position biaryl group axial chiral binaphthyl phosphoramidite ligand and preparation method thereof specifically.
Background technology
The chiral phosphoramidite compounds is the important organic catalysis part of a class, in the asymmetric reaction of metal catalytic, show certain chiral induction ability (Ben.L.Feringa, Acc.Chem.Res.2000,33,346-353).In recent years, some chiral phosphoramidite class parts are designed, be synthesized, utilize the chiral binaphthyl frame design to synthesize chiral phosphoramidite class part (Ben.L.Feringa as people such as Dutch Feringa, et al., J.Org.Chem., 2008,73,940-947), Alexakis etc. then utilize tartaric acid derivatives to synthesize another kind of chiral phosphoramidite class part (Alexandre Alexakis, et al., Tetrahedron:Asymmetry., 2001,12,1151-1157), these chiral ligands have good catalytic activity and enantioselectivity in many asymmetric reactions of metal catalytic.
Learn in the research at the catalysis method of asymmetric synthesis, the design of chiral catalyst and chiral ligand is synthetic to be the most key problem, also is one of active research field the most in the world.Because in the catalysis asymmetric synthesis, only need the catalyzer of minute quantity just can control the chiral product molecule that produces a large amount of required configurations.Very big progress has been obtained in this field in recent years, and all kinds of chiral ligands and catalyzer have reached thousands of, but also has many problems.As: the chiral catalyst of report is applied to the addition reaction of zinc alkyl(s) to α-fork alkene-β-carbonyl carboxylicesters and α-fork allyl two acid esters, and enantioselectivity all is lower than 70%.Therefore, design, synthetic, the new and effective chiral phosphoramidite catalyzer of screening still are necessary.
Summary of the invention
Purpose of the present invention is intended to develop a kind of novel shaft chiral phosphoramidite ligand, and another object of the present invention provides the preparation method of above-mentioned novel phosphoramidite ligand.
3,3 '-position of the present invention contains the axial chiral binaphthyl phosphoramidite ligand of dibenzyl, has the compound of following chemical structure of general formula:
R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, styroyl or α-Jia Bianji in the formula;
Ar is a phenyl, 3,5-3,5-dimethylphenyl, 3, and two (trifluoromethyl) phenyl, 3 of 5-, 5-two-(3, two (trifluoromethyl) phenyl of 5-) phenyl, 3,4,5-trifluorophenyl, 3, two (3,4, the 5-trifluorophenyl) phenyl of 5-, 2-naphthyl, 1-naphthyl, 9-anthryl 9-fluorenes or 9-phenanthryl.
Binaphthyl structure of the present invention is (R) or (S) the axle chirality function base of configuration.
3,3 '-position of the present invention contains the preparation method of the axial chiral binaphthyl phosphoramidite ligand of dibenzyl:
With 3,3 '-duplex aryl-2,2 '-dinaphthol and six alkyl phosphoramidites are 1: 1 by the mole proportioning, in 0-120 ℃, react in organic solvent; After the complete reaction,, obtain the target chiral phosphoramidite ligand through washing, extraction, separation.
Described solvent is ether, tetrahydrofuran (THF), benzene, toluene or dimethylbenzene.
The present invention can also adopt following method: with 3, and 3 '-duplex aryl-2,2 '-dinaphthol and phosphorus trichloride, dialkylamine stepwise reaction after the complete reaction, through washing, extraction, separation, obtain the target chiral phosphoramidite ligand.
Of the present invention 3, the reaction formula of 3-position biaryl group axial chiral binaphthyl phosphoramidite ligand is as follows:
R=methyl, ethyl
R=propyl group, butyl, amyl group, hexyl, benzyl,
Styroyl, α-Jia Bianji
Embodiment
Help further to understand the present invention by following example, but do not limit the present invention.
Example 1: part (R)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-dimethyl phosphoramidite:
Under argon shield; with (R) 3; 3 '-4-phenyl-phenyl-1; 1 '-dinaphthalene-2,2 '-diphenol 591mg (1.0mmol), the inferior phosphoryl triamide 163mg (1.0mmol) of hexamethyl; add in the 20mL Schlenk reaction flask; and add exsiccant toluene 5mL, and heating 110 ℃ of reactions 12 hours, the thin-layer chromatography detection reaction is complete.Reaction mixture is boiled off solvent, and silicagel column separates (petrol ether/ethyl acetate=20/1 is a leacheate) fast, obtains the product of target, 560mg, yield 85.0%.
1H?NMR(500MHz，CDCl
3)，δppm：2.48(s，6H，2×CH
3)，7.25(s，8H，Ar-H)，7.30(m，2H，Ar-H)，7.35(m，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.48(d，J＝8.5Hz，2H，Ar-H)，7.63(d，J＝8.5Hz，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.80(m，2H，Ar-H)，8.40(d，J＝8.5Hz，2H，Ar-H)。
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl carboxylicesters, makes adduct, and yield 78%, enantioselectivity ee value reach 80%.
Example 2: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-dimethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and hexamethyl is a raw material, is solvent with toluene, temperature of reaction is 110 ℃, synthetic respective ligand, yield 83%.
1H?NMR(500MHz，CDCl
3)，δppm：2.47(s，6H，2×CH
3)，7.25(s，8H，Ar-H)，7.32(m，2H，Ar-H)，7.38(m，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.48(d，J＝8.5Hz，2H，Ar-H)，7.65(d，J＝8.5Hz，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.81(m，2H，Ar-H)，8.41(d，J＝8.5Hz，2H，Ar-H)。
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork allyl two acid esters, makes adduct, and yield 80%, enantioselectivity ee value reach 85%.
Example 3: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with benzene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 76%.
1H?NMR(500MHz，CDCl
3)，δppm：1.02(t，6H，2×CH
3)，2.60(dd，J＝8.5Hz，J＝15.5Hz，4H，2×CH
2)，7.25(s，8H，Ar-H)，7.32(m，2H，Ar-H)，7.38(m，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.48(d，J＝8.5Hz，2H，Ar-H)，7.65(d，J＝8.5Hz，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.81(m，2H，Ar-H)，8.41(d，J＝8.5Hz，2H，Ar-H)。
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl carboxylicesters, makes adduct, and yield 92%, enantioselectivity ee value reach 82%.
Example 4: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-dipropyl phosphoramidite:
Under argon shield, in 20mL Schlenk reaction flask, add di-n-propyl amine 111mg (1.1mmol) and exsiccant tetrahydrofuran (THF) 5mL, be cooled to-40 ℃, drip the n-butyllithium solution 0.8mL of 1.5M, reacted 2 hours, stand-by.With (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2; 2 '-diphenol 591mg (1.0mmol) adds in another 20mL Schlenk reaction flask, and adds exsiccant ether 5mL, is cooled to-78 ℃; drip phosphorus trichloride 137mg (1.0mmol), finish, reacted 3 hours; rise to room temperature, reaction system is filtered under argon shield, use the tetrahydrofuran (THF) washing precipitation; filtrate is chilled to-40 ℃; drip the amido lithium solution that has made, rise to room temperature reaction and spend the night, the thin-layer chromatography detection reaction is complete.Reaction mixture is boiled off solvent, and silicagel column separates (petrol ether/ethyl acetate=20/1 is a leacheate) fast, obtains the product of target, 305mg, yield 45%.
1H?NMR(500MHz，CDCl
3)，δppm：0.98(t，6H，2×CH
3)，1.46(m，4H，2×CH
2)，2.55(t，4H，2×CH
2)，7.25(s，8H，Ar-H)，7.32(m，2H，Ar-H)，7.38(m，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.48(d，J＝8.5Hz，2H，Ar-H)，7.65(d，J＝8.5Hz，2H，Ar-H)，7.45(d，J＝8.5Hz，4H，Ar-H)，7.81(m，2H，Ar-H)，8.41(d，J＝8.5Hz，2H，Ar-H)。
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl carboxylicesters, makes adduct, and yield 90%, enantioselectivity ee value reach 88%.
Example 5: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-di-n-butyl phosphoramidite:
With example 4 similar methods, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and di-n-butyl amine are starting raw material, react in tetrahydrofuran (THF), make respective ligand, yield 48%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 98%, enantioselectivity ee value reach 90%.
Example 6: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-two n-pentyl phosphoramidites:
With example 4 similar methods, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and two n-pentyl amine are starting raw material, under 40 ℃, react in tetrahydrofuran (THF), make respective ligand, yield 42%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 88%, enantioselectivity ee value reach 89%.
Example 7: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-di-n-hexyl phosphoramidite:
With example 4 similar methods, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and di-n-hexyl amine are starting raw material, under 60 ℃, react in benzene, make respective ligand, yield 45%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 92%, enantioselectivity ee value reach 91%.
Example 8: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-dibenzyl phosphoramidite:
With example 4 similar methods, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and dibenzyl amine are starting raw material, under 100 ℃, react in toluene, make respective ligand, yield 45%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 80%, enantioselectivity ee value reach 85%.
Example 9: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of N-two styroyl phosphoramidites::
With example 4 similar methods, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and dibenzyl amine are starting raw material, room temperature is reacted in ether, makes respective ligand, yield 48%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 82%, enantioselectivity ee value reach 88%.
Example 10: part (S)-3,3 '-two (4-biphenyl)-2,2 '-dinaphthol-N, the preparation of two ((S)-α-Jia Jibianji) phosphoramidites of N-:
With example 4 similar methods, with (S) 3,3 '-4-phenyl-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and two α-Jia Bianji amine are starting raw material, under 0 ℃, react in ether, make respective ligand, yield 48%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 92%, enantioselectivity ee value reach 80%.
Example 11: part (S)-3,3 '-two (4-(3,5-xylyl benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(3, the 5-3,5-dimethylphenyl)-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with dimethylbenzene, temperature of reaction is 120 ℃, synthetic respective ligand, yield 82%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 90%, enantioselectivity ee value reach 84%.
Example 12: part (S)-3,3 '-two (4-(3,5-dual-trifluoro-p-tolyl benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(3, the 5-bis trifluoromethyl phenyl)-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with toluene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 82%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 98%, enantioselectivity ee value reach 83%.
Example 12: part (S)-3,3 '-two 4-[pair-(3, the 5-dual-trifluoro-p-tolyl) phenyl] and benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3, (3,5-two-(3 for 3 '-4-, two (trifluoromethyl) phenyl of 5-) phenyl)-and phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with benzene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 80%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 88%, enantioselectivity ee value reach 83%.
Example 13: part (S)-3,3 '-two (4-(trifluorophenyl benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(3,4, the 5-trifluorophenyl)-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with toluene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 83%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 86%, enantioselectivity ee value reach 85%.
Example 14: part (S)-3,3 '-two (4-(3, the two trifluoromethyl phenyls of 5-) benzene-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 4 similar methods, with (S) 3,3 '-4-(3, two (3,4, the 5-trifluorophenyl) phenyl of 5-)-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and dibenzyl amine are raw material, are solvent with benzene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 73%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 84%, enantioselectivity ee value reach 90%.
Example 15: part (S)-3,3 '-two-(4-(1-naphthyl) benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(1-naphthyl)-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with toluene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 83%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 98%, enantioselectivity ee value reach 93%.
Example 16: part (S)-3,3 '-two-(4-(2-naphthyl) benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(2-naphthyl)-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with toluene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 83%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 98%, enantioselectivity ee value reach 82%.
Example 17: part (S)-3,3 '-two-(4-(9-anthryl) benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(9-anthryl)-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and two n-pentyl amine are raw material, are solvent with dimethylbenzene, temperature of reaction is 120 ℃, synthetic respective ligand, yield 86%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 89%, enantioselectivity ee value reach 96%.
Example 18: part (S)-3,3 '-two-(4-(9-phenanthryl) benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 1 similar method, with (S) 3,3 '-4-(9-phenanthryl)-phenyl-1,1 '-dinaphthalene-2, the inferior phosphoryl triamide of 2 '-diphenol and Hexaethyl is a raw material, is solvent with dimethylbenzene, temperature of reaction is 120 ℃, synthetic respective ligand, yield 78%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 90%, enantioselectivity ee value reach 82%.
Example 19: part (S)-3,3 '-two-(4-(9-fluorenyl) benzene)-2,2 '-dinaphthol-N, the preparation of N-diethyl phosphoramidite:
With example 4 similar methods, with (S) 3,3 '-4-(9-fluorenyl)-phenyl-1,1 '-dinaphthalene-2,2 '-diphenol and di-n-propyl amine are raw material, are solvent with toluene, temperature of reaction is 100 ℃, synthetic respective ligand, yield 75%.
This part cooperates with copper trifluoromethanesulfcomposite, is used for the conjugate addition reaction of catalysis zinc ethyl and α-fork base-β-carbonyl ester, makes adduct, and yield 86%, enantioselectivity ee value reach 89%.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (5)
1. one kind 3,3 '-position contains the axial chiral binaphthyl phosphoramidite ligand of dibenzyl, it is characterized in that it is the compound with following chemical structure of general formula:
R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, styroyl or α-Jia Bianji in the formula;
Ar is a phenyl, 3,5-3,5-dimethylphenyl, 3, and two (trifluoromethyl) phenyl, 3 of 5-, 5-two-(3, two (trifluoromethyl) phenyl of 5-) phenyl, 3,4,5-trifluorophenyl, 3, two (3,4, the 5-trifluorophenyl) phenyl of 5-, 2-naphthyl, 1-naphthyl, 9-anthryl 9-fluorenes or 9-phenanthryl.
2. the axial chiral binaphthyl phosphoramidite ligand that contains as claimed in claim 1 is characterized in that described binaphthyl structure is (R) or (S) the axle chirality function base of configuration.
3. claim 1 or 3,3 '-position of 2 contain the preparation method of the axial chiral binaphthyl phosphoramidite ligand of dibenzyl, it is characterized in that method is as follows:
With 3,3 '-duplex aryl-2,2 '-dinaphthol and six alkyl phosphoramidites are 1: 1 by the mole proportioning, in 0-120 ℃, react in organic solvent; After the complete reaction,, obtain the target chiral phosphoramidite ligand through washing, extraction, separation.
4. 3,3 '-position as claimed in claim 3 contains the preparation method of the axial chiral binaphthyl phosphoramidite ligand of dibenzyl, it is characterized in that described solvent is ether, tetrahydrofuran (THF), benzene, toluene or dimethylbenzene.
Claim 1 or 23,3 '-position contains the preparation method of the axial chiral binaphthyl phosphoramidite ligand of dibenzyl, it is characterized in that method is as follows: with 3,3 '-duplex aryl-2,2 '-dinaphthol and phosphorus trichloride, dialkylamine stepwise reaction, after the complete reaction,, obtain the target chiral phosphoramidite ligand through washing, extraction, separation.
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| CN103665045A (en) * | 2012-09-14 | 2014-03-26 | 中国科学院兰州化学物理研究所 | Tartaric acid-derived chiral phosphite ligands as well as preparation method and use thereof |
| CN104530122A (en) * | 2015-01-22 | 2015-04-22 | 商丘师范学院 | Dendrimer polymer loaded binaphthol phosphoramidite ligand as well as synthesis method and application thereof |
| CN110548546A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院大连化学物理研究所 | Method for catalyzing asymmetric hydrogenation of imine by iridium/linear phosphine-phosphoramidite system |
| CN113336670A (en) * | 2021-05-28 | 2021-09-03 | 河南大学 | Axial chiral fluorenamine-phenol derivative and preparation method thereof |
| CN114539460A (en) * | 2022-01-24 | 2022-05-27 | 哈尔滨工业大学（深圳） | Method for synthesizing macromolecule loaded asymmetric catalyst |
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2009
- 2009-06-09 CN CNA2009100691935A patent/CN101565436A/en active Pending
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| CN103665045A (en) * | 2012-09-14 | 2014-03-26 | 中国科学院兰州化学物理研究所 | Tartaric acid-derived chiral phosphite ligands as well as preparation method and use thereof |
| CN103665045B (en) * | 2012-09-14 | 2016-03-02 | 中国科学院兰州化学物理研究所 | Chirality phosphite ester ligand that tartrate is derivative and preparation method thereof and purposes |
| CN104530122A (en) * | 2015-01-22 | 2015-04-22 | 商丘师范学院 | Dendrimer polymer loaded binaphthol phosphoramidite ligand as well as synthesis method and application thereof |
| CN110548546A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院大连化学物理研究所 | Method for catalyzing asymmetric hydrogenation of imine by iridium/linear phosphine-phosphoramidite system |
| CN113336670A (en) * | 2021-05-28 | 2021-09-03 | 河南大学 | Axial chiral fluorenamine-phenol derivative and preparation method thereof |
| CN113336670B (en) * | 2021-05-28 | 2023-06-02 | 河南大学 | Axial chiral fluorenamine-phenol derivative and preparation method thereof |
| CN114539460A (en) * | 2022-01-24 | 2022-05-27 | 哈尔滨工业大学（深圳） | Method for synthesizing macromolecule loaded asymmetric catalyst |
| CN114539460B (en) * | 2022-01-24 | 2023-05-02 | 哈尔滨工业大学（深圳） | Synthesis method of macromolecule supported asymmetric catalyst |
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