CN100463720C - Phase-transferring catalyst containing dinaphthalene chiral double-spiral quaternary ammonium and its production - Google Patents
Phase-transferring catalyst containing dinaphthalene chiral double-spiral quaternary ammonium and its production Download PDFInfo
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- CN100463720C CN100463720C CNB2007100577165A CN200710057716A CN100463720C CN 100463720 C CN100463720 C CN 100463720C CN B2007100577165 A CNB2007100577165 A CN B2007100577165A CN 200710057716 A CN200710057716 A CN 200710057716A CN 100463720 C CN100463720 C CN 100463720C
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Abstract
The invention is concerned with chiral bis-spironaphthoxazine ammonium salt phase-transfer activator and its produce method. The 3, 3'-disubstitute-2, 2'-bihalogenated methyl-1, 1' binaphthalene react with 4, 4'-bipiperazine alkane in organic solvent with alkali at 0 to 120 degree to get the aimed chiral bis-spironaphthoxazine ammonium salt phase-transfer activator after washing, extraction and separation. The mol ratio of 3, 3'-disubstitute-2, 2'-bihalogenated methyl-1, 1' binaphthalene, 4, 4'-bipiperazine alkane and alkali is 2:1:2 to 8. This activator can be used to catalyse the conjugate addition reaction of nitroparaffin and alpha, beta-unsubstituted carbonyl compounds with 90 to 99 percent of productivity and the the ee value of reflection selectivity is 60 to 97 percent.
Description
Technical field
The present invention relates to the two spiro quaternary ammonium salt phase transfer catalysts of a class novel chiral, is to disclose a class to contain two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl and preparation method thereof specifically.
Background technology
The chiral quaternary ammonium salt compounds is the important organic molecule phase transfer catalyst of a class, in a lot of catalysis asymmetric reactions, show very high chiral induction ability (O ' Donnell, M.J.In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I., Ed.; WILEY-VCH:New York, 2000; Chapter 10. (b) Shioiri, T.In Handbook ofPhase-Transfer Catalysis; Sasson, Y., Neumann, R., Eds.; Blackie Academic ﹠amp; Professional:London, 1997; Chapter 14. (c) O ' Donnell, M.J.Phases-The Sachem Phase Transfer CatalysisReview; 1998; Issue 4, p5. (d) O ' Donnell, M.J.Phases-The Sachem Phase Transfer CatalysisReview; 1999; Issue 5, p5. (e) Shioiri, T.; Arai, S.InStimulating Concepts in Chemistry; Vogtle, F., Stoddart, J.F., Shibasaki, M., Eds.; WILEY-VCH:Weinheim, 2000; P123. (f) O ' Donnell, M.J.Aldrichimica Acta 2001,34,3.).Recently, many new chiral quaternary ammonium salt class catalyst are designed, are synthesized, as dinaphthalene list spiro quaternary ammonium salt (Chem.Rev.2003,103,3013 of Maruoka; J.Am.Chem.Soc.2007,129,1038), Shibasaki is synthetic bi-quaternary ammonium salt (the Tetrahedron Lett.2002 of frame design with chirality tartaric acid, 43,9539), the ring guanidine quaternary ammonium salt (Angew.Chem. of Nagasawa, Int.Ed.2002,41,2832; Tetrahedron 2001,57, and 8959.), Jew designs the synthetic second generation two quinine phase transfer catalyst (Chem.Commun.2001,1244 on first generation quinine phase transfer catalyst basis; Tetrahedron Lett.2001,42,4645), these chiral quaternary ammonium salt class phase transfer catalysts, in various asymmetric reactions, have good catalytic activity and enantioselectivity (Domenico Albancsc, Mini-Reviews in Organic Chemistry, 2006,3,195-217).
The chiral quaternary ammonium salt compounds is as phase transfer catalyst, be used for the catalysis asymmetric reaction, although people have done a large amount of research work, but be to use existing chiral quaternary ammonium salt class phase transfer catalyst to present high activity and enantioselectivity, can not obtain ideal results all substrates to specific substrates.Therefore, research and development are novel, chiral quaternary ammonium salt class phase transfer catalyst is necessary efficiently.
Summary of the invention
Purpose of the present invention is intended to develop the two spiro quaternary ammonium salt phase transfer catalysts of a kind of novel chiral, and another object of the present invention provides the preparation method of above-mentioned novel two spiro quaternary ammonium salt phase transfer catalysts of chirality.
The two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl that contain of the present invention is characterized in that it is the compound with following chemical structure of general formula:
R is H, phenyl, 3 in the formula, 5-3,5-dimethylphenyl, 3, and 5-bis trifluoromethyl phenyl, 4-nitrobenzophenone, 3,5-is two-(3.5-bis trifluoromethyl phenyl) phenyl, 4-xenyl, 2-naphthyl or 1-naphthyl: n=0,1,2,3,4,5 or 6; X is a fluorine, chlorine, bromine or iodine.
Binaphthyl structure is (R) or (S) the axle chirality function base of configuration.
The preparation method who contains the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl of the present invention, its feature is as follows:
With 3,3 '-disubstituted-2,2 '-two halogenated methyls-1,1 '-dinaphthalene, in 0-120 ℃ under base catalysis, in organic solvent, with 4, after 4 '-two piperazine alkane complete reactions,, obtain the two spiro quaternary ammonium salt phase transfer catalysts of target chirality through washing, extraction, separation; 3,3 '-disubstituted-2,2 '-two halogenated methyls-1,1 '-dinaphthalene and 4, the mole proportioning of 4 '-two piperazine alkane and alkali is 2:1:2～8.
Described solvent is carrene, chloroform, tetrachloromethane, ether, oxolane, benzene,toluene,xylene, acetonitrile or ethyl acetate.
Described alkali is sodium carbonate, potash, cesium carbonate, lithium hydroxide, NaOH, potassium hydroxide or cesium hydroxide.
The two spiro quaternary ammonium salt phase transfer catalysts of chirality of the present invention can be used for the catalysis nitroparaffins to α, the conjugate addition reaction of beta-unsaturated carbonyl compound, and high yield 90-99%, high enantioselectivity ee value reach 60-97% and make addition compound product.
The specific embodiment
Help further to understand the present invention by following example, but do not limit the present invention.
Example 1: Preparation of catalysts: (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine alkane ammonium bromide
Will (R, R)-1,1 '-dinaphthalene-2,2 '-dimethyl bromine 660mg, (1.4mmol), 4,4 '-Lian piperazine 169mg (0.7mmol), potash 580mg, (4.2mmol) add in the 100mL round-bottomed flask, and add the 15mL acetonitrile, the round-bottomed flask mouth connects the spherical condensating tube that has drying tube, heat 80 ℃ and refluxed 24 hours, the thin-layer chromatography detection reaction is complete.Reactant liquor is poured in the beaker that fills 40mL water, stirred 10 minutes.Transfer in the separatory funnel, divide three extractions with the 120mL carrene.Merge organic facies, anhydrous magnesium sulfate drying.Filter, boil off solvent, silicagel column separates (methylene chloride=50/1 is a leacheate) fast, obtain target (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine alkane ammonium bromide catalyst, 527mg, yield 85.0%.
1H NMR (500MHz, CDCl
3), δ ppm:1.73-1.78 (m, 2XCH, 2H), 1.80-1.88 (m, 2XCH, 2H), 2.05-2.22 (m, 2XCH, 2H), 2.30-2.33 (m, 2XCH, 2H), 2.35-2.37 (m, 2XCH, 2H) .3.37-3.42 (m, 2XCH, 2H), 3.52-3.55 (m, 2XCH, 2H), and 3.63-3.74 (m, 6XCH, 6H), 3.96 (d, J=13.0Hz, 2H), 4.50 (d, J=13.0Hz, 2H), 5.09 (d, J=13.0Hz, 2H), 7.38-7.48 (m, Ar-H, 8H), and 7.62-7.65 (m, Ar-H, 4H), 7.84-7.91 (m, Ar-H, 4H), 8.11-8.13 (m, Ar-H, 4H), and 8.22-8.24 (m, Ar-H, 4H).
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 90%, enantioselectivity ee value reach 60%.
Example 2: Preparation of catalysts: (S, S)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ammonium bromide
With example 1 similar method, with (S, S)-1,1 '-dinaphthalene-2,2 '-dimethyl bromine are raw material, with the oxolane is solvent, and reaction temperature is 0 ℃, synthetic (S, S)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ammonium bromide, yield 91.2%.
1H?NMR(500MHz，CDCl
3)，δ?ppm：1.72-1.77(m，2XCH，2H)，1.81-1.88(m，2XCH，2H)，2.10-2.22(m，2XCH，2H)，2.29-2.33(m，2XCH，2H)，2.35-2.37(m，2XCH，2H)，3.37-3.42(m，2XCH，2H)，3.52-3.55(m，2XCH，2H)，3.63-3.74(m，6XCH，6H)，3.96(d，J＝13.0Hz，2H)，4.50(d，J＝13.0Hz，2H)，5.09(d，J＝13.0Hz，2H)，7.38-7.48(m，Ar-H，8H)，7.62-7.65(m，Ar-H，4H)，7.83-7.91(m，Ar-H，4H)，8.12-8.13(m，Ar-H，4H)，8.22-8.25(m，Ar-H，4H)。
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 92%, enantioselectivity ee value reach 57%.
Example 3: Preparation of catalysts: (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-two piperazine methane Australia ammonium
With example 1 similar method, with 4,4 '-two piperazine methane are starting material, 25 ℃ of reactions, with 1.4mmol sodium carbonate is alkali, is solvent with the chloroform, synthetic (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-two piperazine methane ammonium bromides, yield 88.3%.
1H?NMR(500MHz，CDCl
3)，δ?ppm：1.19-1.22(m，CH2，2H)，1.72-1.77(m，2XCH，2H)，1.81-1.88(m，2XCH，2H)，2.10-2.22(m，2XCH，2H)，2.29-2.33(m，2XCH，2H)，2.35-2.37(m，2XCH，2H)，3.37-3.42(m，2XCH，2H)，3.52-3.55(m，2XCH，2H)，3.63-3.74(m，6XCH，6H)，3.96(d，J＝13.0Hz，2H)，4.50(d，J＝13.0Hz，2H)，5.09(d，J＝13.0Hz，2H)，7.38-7.48(m，Ar-H，8H)，7.62-7.65(m，Ar-H，4H)，7.83-7.91(m，Ar-H，4H)，8.12-8.13(m，Ar-H，4H)，8.22-8.25(m，Ar-H，4H)。
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 97%, enantioselectivity ee value reach 63%.
Example 4: Preparation of catalysts: (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ethane ammonium bromide
With example 1 similar method, with 4,4 '-Lian piperazine ethane is raw material, and toluene is solvent, at 110 ℃, be alkali with 2.1mmol potassium hydroxide, synthetic (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ethane ammonium bromide, yield 94.2%.
1H?NMR(500MHz，CDCl
3)，δ?ppm：1.20-1.28(m，2XCH2，4H)，1.72-1.77(m，2XCH，2H)，1.81-1.88(m，2XCH，2H)，2.10-2.22(m，2XCH，2H)，2.29-2.33(m，2XCH，2H)，2.35-2.37(m，2XCH，2H)，3.37-3.42(m，2XCH，2H)，3.52-3.55(m，2XCH，2H)，3.63-3.74(m，6XCH，6H)，3.96(d，J＝13.0Hz，2H)，4.50(d，J＝13.0Hz，2H)，5.09(d，J＝13.0Hz，2H)，7.38-7.48(m，Ar-H，8H)，7.62-7.65(m，Ar-H，4H)，7.83-7.91(m，Ar-H，4H)，8.12-8.13(m，Ar-H，4H)，8.22-8.25(m，Ar-H，4H)。
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 95%, enantioselectivity ee value reach 78%.
Example 5: Preparation of catalysts: (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine propane ammonium bromide
With example 1 similar method, 4,4 '-Lian piperazine propane is raw material, is solvent with carrene, at 40 ℃, be alkali with the 2.8mmol cesium hydroxide, synthetic (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 ' connection piperazine propane ammonium bromide, yield 89.1%.
1H?NMR(500MHz，CDCl
3)，δ?ppm：1.24-1.34(m，3XCH
2，6H)，1.72-1.77(m，2XCH，2H)，1.81-1.88(m，2XCH，2H)，2.10-2.22(m，2XCH，2H)，2.29-2.33(m，2XCH，2H)，2.35-2.37(m，2XCH，2H)，3.37-3.42(m，2XCH，2H)，3.52-3.55(m，2XCH，2H)，3.63-3.74(m，6XCH，6H)，3.96(d，J＝13.0Hz，2H)，4.50(d，J＝13.0Hz，2H)，5.09(d，J＝13.0Hz，2H)，7.38-7.48(m，Ar-H，8H)，7.62-7.65(m，Ar-H，4H)，7.83-7.91(m，Ar-H，4H)，8.12-8.13(m，Ar-H，4H)，8.22-8.25(m，Ar-H，4H)。
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 95%, enantioselectivity ee value reach 75%.
Example 6: Preparation of catalysts: (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine hexane ammonium bromide
With example 1 similar method, with-4,4 '-Lian piperazine hexane is a raw material, and dimethylbenzene is solvent, at 120 ℃ of 3.5mmol cesium hydroxides is alkali, make (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine hexane ammonium bromide, yield 77.3%.
Example 7: Preparation of catalysts: (R, R)-two (3,3 '-diphenyl 1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ethane ammonium bromide
With example 1 similar method, with (R, R)-two (3,3 '-diphenyl-1,1 '-dinaphthalene-2,2 '-methylene bromine are initiation material, 4.2mmol potash is alkali, 80 ℃ of backflows make (R in acetonitrile, R)-two (3,3 '-diphenyl-1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ethane ammonium bromide, yield 69.5%.
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 95%, enantioselectivity ee value reach 88%.
Example 8: Preparation of catalysts: (R, R)-two [3,3 '-two (3, the 5-bis trifluoromethyl phenyl)-1,1 '-dinaphthalene-2,2 '-benzylidene aminos]-4,4 '-Lian piperazine ethane ammonium bromide
With example 1 similar method, 80 ℃ of backflows in acetonitrile, raw materials used is (R, R)-two [3,3 '-two (3, the 5-bis trifluoromethyl phenyl)-1,1 '-dinaphthalene-2,2 '-METHYLENE CHLORIDE makes (R, R)-two [3,3 '-two (3, the 5-bis trifluoromethyl phenyl)-1,1 '-dinaphthalene-2,2 '-benzylidene amino]-4,4 '-Lian piperazine ethane chlorination ammonium, yield 82.0%.
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 95%, enantioselectivity ee value reach 97%.
Example 9: Preparation of catalysts: (R, R)-two [3,3 '-two (3,4, the 5-trifluorophenyl)-1,1 '-Lian Cai-2,2 '-benzylidene aminos]-4,4 '-Lian piperazine ethane ammonium bromide
With example 1 similar method, be solvent with dimethylbenzene, 120 ℃ of reactions, raw materials used is (R, R)-two [3,3 '-two (3,4, the 5-trifluorophenyl)-1,1 '-dinaphthalene-2,2 '-methylene iodine, make (R, R)-two [3, two (3,4,5 trifluorophenyls)-1,1 '-dinaphthalene-2,2 '-benzylidene amino]-4,4 '-Lian piperazine ethane ammonium bromide, yield 80.4%.
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 93%, enantioselectivity ee value reach 96%.
Example 10: Preparation of catalysts: (R, R)-two [3,3 '-two (α-naphthalene)-1,1 '-dinaphthalene-2,2 '-benzylidene aminos]-4,4 '-Lian piperazine ethane ammonium bromide
With example 1 similar method, raw materials usedly be (R, R)-two [3,3 '-two (α-naphthalene)-1,1 '-dinaphthalene-2,2 '-methylene bromine, make (R, R)-two [3,3 '-two (α-naphthalene)-1,1 '-dinaphthalene-2,2 '-benzylidene amino]-4,4 '-Lian piperazine ethane ammonium bromide, again this compound is dissolved in the acetone, add KF, stirring at room 3 days is used diatomite filtration, boil off solvent, obtain (R, R)-two [3,3 '-two (α-naphthalene)-1,1 '-dinaphthalene-2,2 '-benzylidene amino]-4,4 '-Lian piperazine ethane ammonium fluoride, yield 42.3%.
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 93%, enantioselectivity ee value reach 94%.
Example 11: Preparation of catalysts: (R, R)-two [3,3 '-two (4 '-xenyl)-1,1 '-dinaphthalene-2,2 '-benzylidene aminos]-4,4 '-Lian piperazine ethane ammonium bromide
With example 1 similar method, raw materials usedly be (R, R)-two [3,3 '-two (4 '-xenyl)-1,1 '-dinaphthalene-2,2 '-methylene bromine, with ethyl acetate is solvent, under 60 ℃, makes (R, R)-two [3,3 '-two (4 '-xenyl)-1,1 '-dinaphthalene-2,2 '-benzylidene amino]-4,4 '-Lian piperazine ethane ammonium bromide, yield 62.3%.
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 96%, enantioselectivity ee value reach 97%.
Example 12: Preparation of catalysts: (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ethane chlorination ammonium
With example 1 similar method, with (R, R)-two (1,1 '-dinaphthalene-2,2 '-METHYLENE CHLORIDE and 4,4 '-Lian piperazine ethane is raw material, with the chloroform is solvent, and the 5.6mmol lithium hydroxide is an alkali, room temperature reaction, make (R, R)-two (1,1 '-dinaphthalene-2,2 '-benzylidene amino)-4,4 '-Lian piperazine ethane chlorination ammonium, yield 68.2%.
This catalyst is used for the different propane hydrocarbon of catalysis nitro to α, and the conjugate addition reaction of beta-unsaturated carbonyl compound makes addition compound product, and yield 90%, enantioselectivity ee value reach 66%.
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 (7)
1. one kind contains the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl, it is characterized in that it is the compound with following chemical structure of general formula:
R is H, phenyl, 3 in the formula, 5-3,5-dimethylphenyl, 3, and 5-bis trifluoromethyl phenyl, 4-nitrobenzophenone, 3,5-is two-(3, the 5-bis trifluoromethyl phenyl) phenyl, 4-xenyl, 2-naphthyl or 1-naphthyl; N=0,1,2,3,4,5 or 6; X is a fluorine, chlorine, bromine or iodine.
2. the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl that contain as claimed in claim 1 is characterized in that described binaphthyl structure is the axle chirality function base of R configuration.
3. the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl that contain as claimed in claim 1 is characterized in that described binaphthyl structure is the axle chirality function base of S configuration.
4. as claim 1, the 2 or 3 described preparation methods that contain the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl, it is characterized in that method is as follows:
With 3,3 '-disubstituted-2,2 '-two halogenated methyls-1,1 '-dinaphthalene, in 0-120 ℃ under base catalysis, in organic solvent, with 4, after 4 '-two piperazine alkane complete reactions,, obtain the two spiro quaternary ammonium salt phase transfer catalysts of target chirality through washing, extraction, separation; 3,3 '-disubstituted-2,2 '-two halogenated methyls-1,1 '-dinaphthalene and 4, the mole proportioning of 4 '-two piperazine alkane and alkali is 2:1:2～8.
5. as claim 1, the 2 or 3 described preparation methods that contain the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl, it is characterized in that method is as follows:
With 3,3 '-disubstituted-2,2 '-two halogenated methyls-1,1 '-dinaphthalene, in 0-120 ℃ under sodium carbonate, potash or cesium carbonate catalysis, in organic solvent, with 4, after 4 '-two piperazine alkane complete reactions,, obtain the two spiro quaternary ammonium salt phase transfer catalysts of target chirality through washing, extraction, separation; 3,3 '-disubstituted-2,2 '-two halogenated methyls-1,1 '-dinaphthalene and 4, a kind of mole proportioning of 4 '-two piperazine alkane and sodium carbonate, potash or cesium carbonate is 2:1:2～8.
6. as claim 4 or the 5 described preparation methods that contain the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl, it is characterized in that described solvent is carrene, chloroform, tetrachloromethane, ether, oxolane, benzene,toluene,xylene, acetonitrile or ethyl acetate.
7. the preparation method who contains the two spiro quaternary ammonium salt phase transfer catalysts of axial chiral binaphthyl as claimed in claim 4 is characterized in that described alkali is lithium hydroxide, NaOH, potassium hydroxide or cesium hydroxide.
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| GB856247A (en) * | 1958-01-17 | 1960-12-14 | Ici Ltd | Improvements in and relating to filtration processes |
| JP2001048866A (en) * | 1999-06-04 | 2001-02-20 | Nagase & Co Ltd | OPTICALLY ACTIVE TERTIARY AMMONIUM SALT HAVING AXIAL ASYMMETRY, ITS PRODUCTION AND APPLICATION TO ASYMMETRICAL SYNTHESIS OF alpha-AMINO ACID DERIVATIVE |
| CN1951945A (en) * | 2005-10-20 | 2007-04-25 | 中国科学院大连化学物理研究所 | Phosphine-phosphoramidite ligand, its preparation method and uses |
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| GB856247A (en) * | 1958-01-17 | 1960-12-14 | Ici Ltd | Improvements in and relating to filtration processes |
| JP2001048866A (en) * | 1999-06-04 | 2001-02-20 | Nagase & Co Ltd | OPTICALLY ACTIVE TERTIARY AMMONIUM SALT HAVING AXIAL ASYMMETRY, ITS PRODUCTION AND APPLICATION TO ASYMMETRICAL SYNTHESIS OF alpha-AMINO ACID DERIVATIVE |
| CN1951945A (en) * | 2005-10-20 | 2007-04-25 | 中国科学院大连化学物理研究所 | Phosphine-phosphoramidite ligand, its preparation method and uses |
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