CN1884290A - Phosphorus-oxazoline ligand with spiro backbone and its uses in asymmetrical catalytic hydrogenation - Google Patents
Phosphorus-oxazoline ligand with spiro backbone and its uses in asymmetrical catalytic hydrogenation Download PDFInfo
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Abstract
The invention relates to a new chiral toroid phosphine oxazoline ligand and its ionic iridium complex compound, and the application of said iridium complex compound in asymmetric catalytic hydrogenization for imines. The toroid phosphine oxazoline ligand is a widely used compound, for example, used as chiral ligand for asymmetric catalytic hydrogenization; especially said iridium complex compound is characterized by high stereoselectivity for asymmetric catalytic hydrogenization, the ee value reaches 97% and high reactive activity.
Description
Technical field
The present invention relates to the synthetic method of a kind of novel chiral volution Lin — oxazoline part and ionic type iridium complex compound thereof, and the application of ionic type iridium complex compound in the asymmetric catalytic hydrogenation of imines of this Lin — oxazoline part.
Background technology
Asymmetry catalysis is synthetic to be focus (Ohkuma, T. in the current Synthetic Organic Chemistry research field; Kitamura, M.; Noyori, R.Catalytic Asymmetric Synthesis, Wiley, New York, 2000).Asymmetry catalysis synthetic key is how to design and synthesize the chiral catalyst of high enantioselectivity and catalytic activity.The design of chiral catalyst and synthetic is exactly the design of chiral ligand and synthetic, because chiral ligand is the source that chiral catalyst produces asymmetric induction and control in some sense.1966, Wilkinson found that this high reactivity homogeneous catalyst of triphenylphosphine rhodium complex provides prerequisite (Osborn, J.A. for the development of asymmetric catalytic hydrogenation; Jardine, F.H.; Young, J.F.; Wilkinson, G.J.Chem.Soc.A 1966,1711).Nineteen sixty-eight, Knowles and Horner introduce chiral monophosphorus ligand the Wilkinson catalyst system first, have realized the asymmetric catalytic hydrogenation of alkene, have obtained enantioselectivity (Knowles, the W.S. of 3-15%ee; Sabacky, M.J.J.Chem.Soc., Chem.Commun.1968,1445; Horner, L.; Siegel, H.; Buthe, H.Angew.Chem.Int.Ed.1968,7,942).1975, Knowles synthesized biphosphine ligand DIPAMP, and this part successfully is used for industrial production L-Dopa (a kind of specifics for the treatment of Parkinsonism) (Vineyard, B.D.; Knowles, W.S.; Sabacky, M.J.; Bachman, G.L.; Weinkauff, D.J.J.Am.Chem.Soc.1977,99,5946; Knowles, W.S.Acc.Chem.Res.1983,16,106; Knowles, W.S.J.Chem.Ed.1986,63,222).Through nearly 40 years development, people develop plurality of ligand, have wherein much obtained good application in hydrogenation.But because the specificity of catalytic hydrogenation, every kind of part can only be effective to a class or several class substrate, a lot of substrates are still arranged at present, hydrogenation such as some group with imine moiety also is not well solved, therefore be necessary to develop more effectively chiral ligand and catalyzer thereof, realize the high enantioselective hydrogenation of these substrates.By Pfaltz, Helmchen and Williams have been subjected to common concern (von Matt, P. at the phosphine-oxazoline class part of difference independent development in 1993; Pfaltz, A.Angew.Chem.Int.Ed.1993,32,566; Sprinz, J.; Helmchen, G.Tetrahedron Lett.1993,34,1769; Dawson, G.L.; Frost, C.G.; Williams, J.M.J.; Coote, S.J.Tetrahedron Lett.1993,34,3149.).This class part often shows higher activity in asymmetric hydrogenation of imines reaction, but can only provide medium enantioselectivity (Schnider, P.; Koch, G.; Pretot, R.; Wang, G.; Bohnen, M.; Kruger, C.; Pfaltz, A.Chem.Eur.J.1997,3,887.), therefore effective more Lin — oxazoline part of exploitation and catalyzer have important use value for the asymmetric hydrogenation of imine compound.
Summary of the invention
For solving the problems of the prior art, propose the objective of the invention is:
1) provides a kind of novel volution Lin — oxazoline part and ionic type iridium complex compound thereof with spiro indan structure.
2) provide a kind of novel volution Lin — oxazoline part and the synthetic method of ionic type iridium complex compound thereof with spiro indan structure.
3) provide the above-mentioned novel volution Lin — oxazoline part and the purposes of ionic type iridium complex compound thereof with spiro indan structure, promptly in the asymmetric catalytic hydrogenation of imines as catalyzer.
For realizing purpose of the present invention, New-type spiro Lin — oxazoline part disclosed by the invention and ionic type iridium complex compound thereof have following structural formula:
Wherein: R
1Be C
1～C
6Alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
6Alkyl,-oxyl and halo alkyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl, benzyl; Described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl; Described-oxyl is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy; R
2Be C
1～C
6Alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
6Alkyl,-oxyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl, 2-furyl, benzyl; X is a hexafluoro-phosphate radical, hexafluoro tellurate radical, tetrafluoroborate, tetraphenyl borate, four-(3,5-two trifluoromethyls) borates.
The synthetic method of New-type spiro Lin — oxazoline part disclosed by the invention and corresponding ionic type iridium complex compound, be by optically pure 1,1 '-spiro indan-7,7 '-diphenol sets out through synthetic a series of different volution Lin — oxazoline parts of multistep and corresponding ionic type iridium complex compound.Its building-up process can be represented with following reaction formula:
New-type spiro Lin — oxazoline part provided by the present invention and corresponding ionic type iridium complex compound thereof are a kind of purposes compounds very widely.For example, this ionic type iridium complex compound is used to contain the catalytic hydrogenation of the latent chipal compounds of carbon-to-nitrogen double bon as catalyzer in solvent.
The present invention has synthesized chiral spiro Lin — oxazoline part first, and as the synthetic corresponding ionic type iridium complex compound of raw material.When the iridium complex of chiral spiro Lin — oxazoline part of the present invention is applied to the asymmetric catalytic hydrogenation of imines, have very high stereoselectivity, the ee value is up to 97%, has high reaction activity advantages such as (finishing hydrogenation under normal pressure) simultaneously concurrently.
Embodiment
New-type spiro Lin — oxazoline part of the present invention is dextrorotation volution Lin — oxazoline part-(R
a, R)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan base-7-]-4-replacement-4,5-dihydro-oxazole or (S
a, R)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan-7-]-4-replacement-4,5-dihydro-oxazole, left-handed volution Lin — oxazoline part-(S
a, S)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan-7-]-4-replacement-4,5-dihydro-oxazole or (R
a, S)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan-7-]-4-replacement-4, the 5-dihydro-oxazole.
Volution Lin — oxazoline part has two kinds of chirality factors: axial chirality and central chirality, so have four optically active isomers, comprising two pairs of enantiomers, promptly the volution skeleton is R
aConfiguration, dihydro-oxazole partly are that S configuration and volution skeleton are S
aConfiguration, dihydro-oxazole partly are a pair of enantiomer that is of R configuration; The volution skeleton is S
aConfiguration, dihydro-oxazole partly are that S configuration and volution skeleton are R
aConfiguration, dihydro-oxazole partly be the R configuration for another to enantiomer.Therefore, in fact the said volution Lin of the present invention — oxazoline part and corresponding ionic type iridium complex compound comprise above-mentioned four kinds of isomer.These isomer have identical chemical structure of general formula, but have different three-dimensional arrangements and rotary light performance.
Synthetic method of the present invention is with optically pure 1,1 '-spiro indan-7,7 '-diphenol is a starting raw material, through becoming ester with trifluoromethanesulfanhydride anhydride, the palladium catalytic coupling, trichlorosilane reduction generation important intermediate 7-diarylphosphino-7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan, this intermediate carries out the catalytic esterification of palladium, and alkaline condition is hydrolyzed into acid, and then becoming acid amides alcohol with the chiral amino of 2 replacements is ethanol condensed, last cyclisation obtains volution Lin — oxazoline part.Then with [Ir (COD) Cl]
2Reaction makes the iridium complex of chiral spiro Lin — oxazoline part.Specify as follows:
1) with 1～2 normal trifluoromethanesulfanhydride anhydride and 1 normal optically pure 1,1 '-spiro indan-7,7 '-diphenol is a raw material, generate corresponding two triflated compound with 2～4 normal pyridines as acid binding agent, temperature of reaction is 0 ℃～25 ℃, and solvent is organic solvents such as methylene dichloride, tetrahydrofuran (THF).
2) will be by 1) the gained compound is at 1 of the palladium of 1～5mol% and 1～6mol%, under the catalysis of 4-two (diphenylphosphino) butane (dppb), with organic amine such as 2～10 normal diisopropyl ethyl amines, n-Butyl Amine 99 and the reaction of 2～4 equivalent diaryl phosphine oxides 1～20 hour, obtain single phosphine substitution product, reaction solvent is dimethyl sulfoxide (DMSO), N, organic solvents such as dinethylformamide, 50～150 ℃ of temperature of reaction.
3) will be by 2) the gained compound is at 20～50 normal diisopropyl ethyl amines, n-Butyl Amine 99, N, under the existence of organic amines such as accelerine, go back original reagent reduction 3～5 days with 10～40 normal trichlorosilanes etc., obtain single phosphine reduzate, reaction solvent is organic solvents such as toluene, dimethylbenzene, and temperature of reaction is 100～150 ℃.
4) will be by 3) the gained compound is at 1 of the palladium of 1～5mol% and 1～6mol%, under the catalysis of 3-two (diphenylphosphino) propane (dppp), with 2～10 normal diisopropyl ethyl amines, n-Butyl Amine 99, N, organic amines such as accelerine and methyl alcohol reacted in carbon monoxide 1～20 hour, obtain monolateral esterification products, reaction solvent is dimethyl sulfoxide (DMSO), N, organic solvents such as dinethylformamide, 50～100 ℃ of temperature of reaction.
5) will be by 4) hydrolysis under 40～60% potassium hydroxide aqueous solution effect of gained esterification products generates acid.Solvent for use is alcoholic solvents such as methyl alcohol, ethanol.Temperature of reaction is 70～120 ℃.
6) will be by 5) products therefrom is at 2～4 normal I-hydroxybenzotriazoles (HOBt) and 3～6 normal N, N-dicyclohexyl carboxamide (DCC) effect obtains the corresponding amide alkylol cpd with the chirality 2-monoethanolamine condensation that 2～4 equivalent 2-replace down, solvent for use is organic solvents such as tetrahydrofuran (THF), dioxane, and temperature of reaction is 0～60 ℃.
7) will be by 6) gained acid amides alkylol cpd is at 5～10% N, under N-dimethyl-4-aminopyridine (DMAP) catalysis, with 2～4 equivalent triethylamines, organic basess such as diisopropyl ethyl amine are as acid binding agent, with 1～1.2 normal methylsulfonyl chloride, chlorination reagent effects such as Tosyl chloride obtain chiral spiro Lin — oxazoline part; Solvent for use is organic solvents such as methylene dichloride, 1,2-ethylene dichloride, and temperature of reaction is 0 ℃～25 ℃.
8) will be by 6) chiral spiro Lin — oxazoline part and 1～2 normal monovalence iridic compound be as [Ir (COD) Cl]
2(COD=1,5-cyclooctadiene), and 1～3 normal sodium salt reaction that has different anions obtained corresponding ionized catalyst in 3～24 hours; Solvent for use is organic solvents such as methylene dichloride, 1,2-ethylene dichloride, and temperature of reaction is 20～50 ℃.
The ionic type iridium complex compound is used to contain the catalytic hydrogenation of the latent chipal compounds of carbon-to-nitrogen double bon as catalyzer in solvent; Described solvent is chloroparaffin, benzene, toluene or ether solvent; Catalyst levels is 1%～0.01%, and temperature of reaction is 0～40 ℃, and the reaction times is 6 hours～48 hours;
Wherein:
It is R that this iridium catalyst is used for molecular formula
4R
5C=NR
3The catalytic hydrogenation of imines the time have very high stereoselectivity, the ee value is up to 97%, has high reaction activity simultaneously, just can finish characteristics such as this conversion under normal pressure.In the formula, R
3, R
4, R
5Be alkyl (C
1～C
6), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
6Alkyl,-oxyl and halogen, replacing radix is 1～5), substituting groups such as 1-naphthyl, 2-naphthyl, furyl, thienyl, R
3, R
4, R
5Can be identical, also can be different; Described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl etc., and described-oxyl is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.
Catalytic hydrogenation process to imines specifies as follows:
Under argon gas or nitrogen protection, catalyzer and substrate are added in the reactor in the pipe, add degassing solvent, to tighten reactor and, fill hydrogen pressure to required pressure with the careful displacement of hydrogen 3～5 times, stirring reaction is to finishing.Catalyst levels is 1%～0.01%, hydrogen pressure 1～100atm, and temperature of reaction is 0～60 ℃, and the reaction times is 6 hours～2 days, and reaction solvent is chloroparaffin, benzene, toluene or ether solvent, as: ether, t-butyl methyl ether etc.
To help a nearly step to understand the present invention by following embodiment of the present invention, but not limit content of the present invention.Preparation method of the present invention can be further as follows with the preparation process embodiment of representation compound:
Embodiment 1:(S)-7,7 '-two (trifluoro-methanesulfonyl oxy)-1,1 '-preparation of spiro indan
Adding (S)-1,1 in the 250mL reaction flask '-spiro indan-7,7 '-diphenol (5.0g, 19.8mmol), pyridine (7.0mL, 86.7mmol) and the 100mL methylene dichloride, cryosel is bathed and is chilled to below 0 ℃, by the constant pressure funnel temperature control drip trifluoromethanesulfanhydride anhydride (8.2mL, 43.7mmol).Finish, be warming up to room temperature naturally and stir and spend the night.Rotary evaporation precipitation, resistates 80mL acetic acid ethyl dissolution is transferred to separating funnel, uses 5%HCl solution, saturated aqueous common salt, saturated NaHCO
3Solution, saturated aqueous common salt washs successively, anhydrous Na
2SO
4Dry.After filtering, sloughing solvent, an amount of methylene dichloride dissolving is crossed the silica gel short column, eluent methylene chloride.Slough solvent get (S)-7,7 '-two (trifluoro-methanesulfonyl oxy)-1,1 '-spiro indan 9.9 gram, white solid, yield: 97%.Mp 62-64℃；[α]
20 D-143(c0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ2.35(m，4H，CH
2)，3.10(m，4H，CH
2)，7.15(dd，2H，J＝1.8 and 6.6Hz，Ar-H)，7.26-7.30(m，4H，Ar-H)；
13CNMR(75MHz，CDCl
3)δ31.1，38.6，59.4，115.9，118.5，120.1，124.4，129.4，138.2，145.8，147.7；MS(EI)m/z 516(M
+)；Anal.calcd forC
19H
14F
6O
6S
2：C 43.97(44.19)；H 2.83(2.73)。
Embodiment 2:(S)-7-diphenylphosphine acyl group-7 '-trifluoro-methanesulfonyl oxy-1,1 '-preparation of spiro indan
In the 100mL reaction flask, add (S)-7,7 '-two (trifluoro-methanesulfonyl oxy)-1,1 '-spiro indan (4.0g, 7.75mmol), diphenyl phosphine oxide (3.13g, 15.5mmol), palladium (87mg, 0.39mmol), 1, the basic butane (dppb of 4-two (diphenylphosphine), 166mg, 0.39mmol) and 25mL degassing DMSO.Induction stirring makes its abundant mixing, adds N, the N-diisopropyl ethyl amine (4.1g, 32mmol) after, 100 ℃ of oil bath heating were reacted 6 hours.Be chilled to room temperature, ethyl acetate dilution, separatory, 5%HCl solution, saturated aqueous common salt, saturated NaHCO
3Solution, saturated aqueous common salt washs successively, anhydrous Na
2SO
4Dry.After filtering, sloughing solvent, with the silicagel column column chromatography (leacheate: sherwood oil/EtOAc=3: 1) (S)-7-diphenylphosphine acyl group-7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan 4.0 grams, white solid, yield: 90%.Mp 173-175℃；[α]
8 D-148(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ2.20-2.39(m，4H，CH
2)，3.08(m，2H，CH
2)，3.23-3.41(m，2H，CH
2)，6.21(d，2H，J＝8.1Hz，Ar-H)，7.14-7.20(m，11H，Ar-H)；
31P NMR(121MHz，CDCl
3)δ31.8(s)；
13C NMR(75MHz，CDCl
3)δ21.1，30.8，31.8，39.8，40.1，61.8，117.5，123.9，126.1，128.0，128.2，131.3，131.4，131.7，131.8，133.6，140.7，144.8，146.1，149.8；MS(EI)m/z 569(M+1
+)；Anal.calcd for C
30H
24F
3O
4PS：C 63.47(63.38)；H 4.15(4.25)；S5.45(5.64)。
Embodiment 3:(S)-7-two (p-methoxyphenyl) phosphono-7 '-trifluoro-methanesulfonyl oxy-1,1 '-preparation of spiro indan
With (S)-7,7 '-two (trifluoro-methanesulfonyl oxy)-1,1 '-spiro indan and di-p-methoxy phenyl-phosphonite are feedstock production, method is identical with embodiment 2.Get white solid, yield: 90%.Mp 150-152℃；[α]
8 D-216(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ2.20-2.32(m，3H，CH
2)，3.04-3.18(m，3H，CH
2)，3.20-3.40(m，2H，CH
2)，3.78(s，3H，OCH
3)，3.85(s，3H，OCH
3)，6.24(d，2H，J＝8.1Hz，Ar-H)，6.80-6.85(m，4H，Ar-H)，6.86-7.00(m，2H，Ar-H)，7.16-7.21(m，4H，Ar-H)，7.21-7.30(m，2H，Ar-H)，7.32(d，1H，J＝7.2Hz，Ar-H)；
31PNMR(121MHz，CDCl
3)δ31.45(s)；
13C NMR(75MHz，CDCl
3)δ29.7，30.1，30.8，38.7，38.9，54.2，60.8，112.4，112.6，116.3，118.8，121.1，122.6，124.9，125.1，125.9，126.4，126.9，127.2，127.4，127.8，131.9，132.1，132.4，132.5，139.7，143.8，144.8，145.0，148.6，151.7，160.7，160.9；MS(EI)m/z 628(M
+)；FT-ICRMS(FAB)(calcd for)C
32H
28F
3O
6PS+H
+：629.1362(629.1369)。
Embodiment 4:(S)-7-two (3, the 5-3,5-dimethylphenyl) phosphino--7 '-trifluoro-methanesulfonyl oxy-1,1 '-preparation of spiro indan
With (S)-7,7 '-two (trifluoro-methanesulfonyl oxy)-1,1 '-spiro indan and two (3, the 5-3,5-dimethylphenyl) phosphonous acid is a feedstock production, method is identical with embodiment 2.Get white solid, yield: 92%.Mp 183-185℃；[α]
8 D-256(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ2.18-2.37(m，3H，CH
2)，2.23(s，6H，CH
3)，2.25(s，6H，CH
3)，2.90-3.18(m，3H，CH
2)，3.21-3.42(m，2H，CH
2)，6.26(d，1H，J＝8.1Hz，Ar-H)，6.85(d，2H，J＝12Hz，Ar-H)，6.90-7.10(m，6H，Ar-H)，7.10-7.20(m，2H，Ar-H)，7.39(d，1H，J＝7.8Hz，Ar-H)；
31P NMR(121MHz，CDCl
3)δ31.16(s)；
13C NMR(75MHz，CDCl
3)δ21.4，21.5，21.7，30.9，32.1，39.8，40.5，62.1，115.8，117.4，120.0，123.8，126.2，126.5，127.7，127.9，129.1，129.2，129.5，129.6，130.3，131.6，133.1，133.30，133.4，133.6，135.3，136.7，137.5，137.7，137.8，137.9，140.7，145.1，145.9，146.1，150.3，153.1；FT-ICRMS(FAB)(calcd for)C
34H
32F
3O
4PS+H
+：625.1782(625.1784)。
Embodiment 5:(S)-7-diphenylphosphino-7 '-trifluoro-methanesulfonyl oxy-1,1 '-preparation of spiro indan
Adding (S)-7-diphenylphosphine acyl group-7 in the 100mL reaction flask '-trifluoro-methanesulfonyl oxy-1; 1 '-spiro indan (1.4g; 2.5mmol), diisopropyl ethyl amine (13.2g; 102mmol) and toluene 50mL; after ice bath is chilled to 0 ℃, add under the induction stirring trichlorosilane (4.0mL, 39mmol); remove ice bath, oil bath was heated to 110 ℃ of stirring reactions 5 days.Be chilled to room temperature, the ether dilution, saturated sodium hydroxide solution cancellation reaction, sand core funnel filters, ether washing, anhydrous sodium sulfate drying.After concentrating, silica gel column chromatography (leacheate: sherwood oil/EtOAc=15: 1) (S)-7-diphenylphosphino-7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan (1.26g, 91%), product is a white solid.Mp 72-74℃；[α]
8 D-146(c 0.5，CH
2Cl
2)；
1HNMR(300MHz，CDCl
3)δ7.04-7.28(m，10H，Ar-H)，6.90-7.04(m，5H，Ar-H)，6.65(d，J＝8.1Hz，1H，Ar-H)，3.09(m，4H，CH
2)，2.54(m，1H，CH
2)，2.26-2.33(m，3H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-20.5(s)；
13C NMR(75MHz，CDCl
3)δ29.7，30.3，37.9，39.0，39.1，60.6，114.7，117.3，118.9，123.0，124.5，126.4，126.9，127.1，127.2，127.3，127.7，131.1，131.3，132.1，132.3，132.4，132.7，133.4，134.9，135.1，137.5，137.7，140.9，142.7，142.8，144.5，146.9，151.8；MS(EI)m/z 552(M
+)；Anal.calcd for C
30H
24F
3O
4PS：C 65.20(65.22)；H 4.25(4.38)。
Embodiment 6:(S)-7-two (p-methoxyphenyl) phosphino--7 '-trifluoro-methanesulfonyl oxy-1,1 '-preparation of spiro indan
With (S)-7-two (p-methoxyphenyl) phosphono-7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan is a feedstock production, method is identical with embodiment 5.Colorless oil, room temperature are placed and are solidified yield: 75%.[α]
8 D-144(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ2.24-2.33(m，3H，CH
2)，2.50(m，1H，CH
2)，3.04(m，4H，CH
2)，3.75(s，3H，OCH
3)，3.78(s，3H，OCH
3)，6.70-6.78(m，5H，Ar-H)，6.89-7.00(m，5H，Ar-H)，7.17-7.25(m，4H，Ar-H)；
31P NMR(121MHz，CDCl
3)δ-23.65(s)；
13C NMR(75MHz，CDCl
3)δ29.6，30.1，30.3，38.0，38.6，54.1，60.5，112.3，112.6，112.8，112.9，114.7，118.9，122.9，124.2，126.1，126.3，127.7，128.4，128.5，132.3，132.6，132.7，133.6，133.9，134.1，140.8，142.6，142.7，144.6，146.8，150.8，151.2，158.6，158.9；FT-ICRMS(FAB)(calcd for)C
32H
28F
3O
6PS+H
+：629.1362(629.1369)。
Embodiment 6:(S)-7-two (3, the 5-3,5-dimethylphenyl) phosphino--7 '-trifluoro-methanesulfonyl oxy-1,1 '-preparation of spiro indan
With (S)-7-two (3, the 5-3,5-dimethylphenyl) phosphono-7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan is a feedstock production, method is identical with embodiment 5.Get white solid, yield: 75%.Mp 94-96℃；[α]
8 D-156(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ2.17(s，6H，CH
3)，2.19(s，6H，CH
3)，2.08-2.18(m，3H，CH
2)，2.56(m，1H，CH
2)，3.08(m，4H，CH
2)，6.61-6.70(m，5H，Ar-H)，6.84(s，1H，Ar-H)，6.98(s，1H，Ar-H)，7.00(m，1H，Ar-H)，7.11-7.26(m，4H，Ar-H)；
31P NMR(121MHz，CDCl
3)δ-20.66(s)；
13C NMR(75MHz，CDCl
3)δ20.1，20.2，29.6，30.4，37.9，38.9，60.4，114.6，117.1，118.9，122.9，124.1，126.2，127.3，128.7，129.2，129.8，130.0，130.3，130.7，131.8，132.1，133.3，134.4，134.5，136.1，136.2，136.3，137.2，137.3，140.9，142.7，142.4，144.4，146.9，151.2，151.5；MS(EI)m/z 608(M
+)；Anal.calcd for C
34H
32F
3O
3PS：C 66.87(67.09)；H 5.46(5.30)。
Embodiment 8:(S)-7-diphenylphosphino-7 '-methoxy acyl group-1,1 '-preparation of spiro indan
In the 250mL two-mouth bottle that bleed head and anti-mouthful of plug are housed, add MeOH (60mL), DMSO (90mL) and Et
3N (24mL), after mixing, the degassing is three times under the CO atmosphere.In another one is equipped with the four-necked bottle of induction stirring, anti-mouthful of plug, reflux condensing tube, bleed head and thermometer, add (S)-77a (6.27g, 11.3mmol), Pd (OAc)
2(381.7mg, 1.70mmol) and dppp (701.1mg 1.70mmol), is replaced as the CO atmosphere with system, immediately with double-ended needle with the degassing solution carefully move into.Oil bath is heated to 70 ℃, stirring reaction 4-6hrs, and system is by the orange beige that becomes.TLC follows the tracks of and detects until reacting completely.The decompression precipitation, resistates CH
2Cl
2Again dissolving, silica gel column chromatography, with ethyl acetate/petroleum ether 1: 16 as eluent, compound (S)-7-diphenylphosphino-7 '-methoxy acyl group-1,1 '-spiro indan (4.8g, 91%).Product is a colourless viscous liquid, puts curing for a long time.[α]
20 D-189.0(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.58(d，J＝7.8Hz，1H，Ar-H)，7.41(d，J＝8.4Hz，1H，Ar-H)，7.29-6.87(m，14H，Ar-H)，3.12(s，3H，CH
3)，3.10-2.95(m，4H，CH
2)，2.59-2.48(m，1H，CH
2)，2.30-2.20(m，3H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-20.8(s)；
13CNMR(75MHz，CDCl
3)δ167.2，156.4，156.1，151.2，145.9，144.0，143.9，139.4，139.2，137.0，136.8，134.3，134.0，133.5，133.3，132.0，131.6，131.4，131.2，129.7，128.8，128.5，128.3，128.1，127.7，126.9，126.7，125.5，64.0，51.2，41.0，38.1，31.2，30.8.HRMS(FAB)calcd forC
31H
27O
2P：462.1743，Found 462.1737。
Embodiment 9:(S)-7-two (p-methoxyphenyl) phosphino--7 '-methoxy acyl group-1,1 '-preparation of spiro indan
With (S)-7-two (p-methoxyphenyl) phosphino--7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan is a feedstock production, method is identical with embodiment 8.Get white solid, yield: 85%.Mp 162-163℃；[α]
20 D-165.6(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.61(d，J＝7.5Hz，1H，Ar-H)，7.41(d，J＝7.5Hz，1H，Ar-H)，7.27-7.22(m，2H，Ar-H)，7.08(t，J＝7.5Hz，1H，Ar-H)，6.97-6.78(m，5H，Ar-H)，6.75(t，J＝9.0Hz，4H，Ar-H)，3.78(s，3H，CH
3)，3.74(s，3H，CH
3)，3.11(s，3H，CH
3)，3.08-3.06(m，4H，CH
2)，2.58-2.47(m，1H，CH
2)，2.26-2.16(m，3H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-24.3(s)；
13CNMR(75MHz，CDCl
3)δ167.2，159.8，159.6，155.3，155.0，150.7，145.6，143.7，135.1，134.9，134.6，133.4，132.5，132.2，130.0，129.8，129.2，128.4，128.1，127.9，126.6，126.3，125.0，113.9，113.8，113.7，113.6，63.7，55.2，55.1，50.9，40.3，38.0，31.0，30.6；MS(ESI)m/z 523(M+1，100)；Anal.calcd for C
33H
31O
4P：C 75.85，H 5.98；Found：C 76.04，H 5.93。
Embodiment 10:(S)-7-two (3, the 5-dimethyl) phenyl phosphino--7 '-methoxy acyl group-1,1 '-preparation of spiro indan
With (S)-7-two (3, the 5-3,5-dimethylphenyl) phosphino--7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan is a feedstock production, method is identical with embodiment 8.Get white foam shape solid, yield: 90%.Mp 65-67℃；[α]
20 D-170.4(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.56(d，J＝7.8Hz，1H，Ar-H)，7.42(dd，J＝7.2and 0.9Hz，1H，Ar-H)，7.27-7.12(m，2H，Ar-H)，7.09(t，J＝7.5Hz，1H，Ar-H)，6.97-6.93(m，1H，Ar-H)，6.88(s，1H，Ar-H)，6.82(s，1H，Ar-H)，6.58(dd，J＝9.9and 9.0Hz，4H，Ar-H)，3.09(s，3H，CH
3)，3.06-2.99(m，4H，CH
2)，2.52-2.40(m，2H，CH
2)，2.37-2.29(m，2H，CH
2)，2.21(s，6H，CH
3)，2.16(s，6H，CH
3)；
31P NMR(121MHz，CDCl
3)δ-20.8(s)；
13C NMR(75MHz，CDCl
3)δ166.6，156.3，156.0，151.2，151.1，145.8，143.3，143.2，138.9，138.8，137.2，137.1，137.0，136.0，134.0，132.0，131.8，131.7，131.6，131.0，130.9，130.6，130.1，130.0，129.5，129.4，128.5，127.4，126.3，126.2，124.9，63.9，50.7，40.7，38.3，31.0，30.7，21.4，21.3；MS(ESI)m/z 519(M+1，100)；Anal.calcd for C
35H
35O
2P：C 81.6，H 6.80；Found：C 80.95，H 6.94。
Embodiment 11:(S)-7-diphenylphosphino-7 '-carboxyl-1,1 '-preparation of spiro indan
In 100mL two neck bottles, add (S)-7-diphenylphosphino-7 '-methoxy acyl group-1,1 '-spiro indan (3.0g, 6.49mmol), system replaced nitrogen after, add MeOH (75mL) and stir and make its dissolving.Carefully drip the 40%KOH aqueous solution (15mL) then.Beginning adularescent floss generates, then slowly dissolving.Finish oil bath and be warming up to 100 ℃ system is refluxed slightly, this moment, system became limpid.Keep this thermotonus 24hrs, the TLC tracking monitor is until reacting completely.The frozen water cooling carefully drips concentrated hydrochloric acid to pH 2 down in system, have a large amount of white precipitates to generate.With the dilution of 100mL water, ethyl acetate (100mL * 3) extraction, separatory merges organic phase, with saturated common salt washing, anhydrous Na
2SO
4Dry.Suction filtration is removed siccative, revolves the steaming precipitation, resistates silicagel column column chromatography, with petrol ether/ethyl acetate mixed solvent (5: 1) as eluent, obtain compound (S)-7-diphenylphosphino-7 '-carboxyl-1,1 '-spiro indan (2.88g, 98.8%), is white solid.Mp 202-203℃；[α]
20 D-153.4(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.55-6.82(m，16H，Ar-H)，3.11-3.02(m，4H，CH
2)，2.51-2.17(m，4H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-20.8(s)；
13C NMR(75MHz，CDCl
3)δ170.7，156.8，156.4，152.7，146.2，144.2，144.4，139.7，139.5，136.3，134.2，134.0，133.7，133.4，133.1，130.7，130.3，129.6，128.5，128.4，128.2，127.9，126.8，126.6，126.0，125.3，64.0，41.6，41.5，37.7，31.4，30.9；HRMS(FAB)calcd for C
30H
25O
2P：448.1592；Found 448.1587。
Embodiment 12:(S)-7-diphenylphosphino-7 '-carboxyl-1,1 '-preparation of spiro indan
With (S)-7-two (p-methoxyphenyl) phosphino--7 '-methoxy acyl group-1,1 '-spiro indan is a feedstock production, the KOH aqueous solution with 60% is alkali, method is identical with embodiment 11.Get white solid, yield: 67%.Mp 183-184℃；[α]
20 D-154.8(c 0.5，CH
2Cl
2)；
1HNMR(300MHz，CDCl
3)δ7.58(d，J＝6.9Hz，1H，Ar-H)；7.44(d，J＝7.2Hz，1H，Ar-H)，7.25-7.20(m，2H，Ar-H)，7.03(t，J＝7.5Hz，1H，Ar-H)，6.89-6.66(m，9H，Ar-H)，3.75(d，J＝7.5Hz，6H，CH
3)，3.08-2.98(m，4H，CH
2)，2.49-2.15(m，4H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-24.1(s)；
13C NMR(100MHz，CDCl
3)δ170.5，160.1，159.7，152.4，146.1，143.9，135.4，135.2，134.9，134.7，133.6，132.0，130.4，130.1，129.4，127.5，126.8，125.4，114.1，113.9，64.0，55.3，41.0，37.7，31.3，30.8；MS(ESI)m/z 507(M-1，100)；Anal.calcd for C
32H
29O
4P：C 75.58，H5.75；Found：C 75.00，H 5.95。
Embodiment 13:(S)-7-two (3, the 5-3,5-dimethylphenyl) phosphino--7 '-carboxyl-1,1 '-preparation of spiro indan
With (S)-7-two (3, the 5-3,5-dimethylphenyl) phosphino--7 '-methoxy acyl group-1,1 '-spiro indan is a feedstock production, method is identical with embodiment 11.Get white solid, yield: 90%.Mp 110-112℃；[α]
20 D-143.2(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.49(d，J＝7.8Hz，1H，Ar-H)，7.42(d，J＝7.2Hz，1H，Ar-H)，7.26-7.16(m，2H，Ar-H)；7.04(t，J＝7.5Hz，1H，Ar-H)，6.86-6.80(m，3H，Ar-H)，6.54(dd，J＝15and 7.5Hz，4H，Ar-H)，3.12-3.01(m，4H，CH
2)，2.56-2.19(m，4H，CH
2)，2.15(s，6H，CH
3)，2.10(s，6H，CH
3)；
31P NMR(121MHz，CDCl
3)δ-20.6(s)；
13C NMR(100MHz，CDCl
3)δ170.3，156.1，155.7，152.4，146.1，146.0，143.7，143.6，139.0，138.8，137.2，137.1，135.7，135.6，133.8，131.7，131.5，130.8，130.0，129.9，129.5，129.1，126.3，124.7，63.8，41.3，41.2，37.9，31.2，30.7，21.3，21.2；HRMS(EI)calcd for C
34H
33O
2P：504.2218；Found 504.2223。
Embodiment 14:(S
a, S)-7 '-diphenylphosphino-[1,1 ']-spiro indan-7-[N-(1-methylol-2-methyl-propyl)]-preparation of methane amide
Be equipped with in the two neck bottles of anti-mouthful of fill in, bleed head and induction stirring at 100mL, take by weighing (S)-7-diphenylphosphino-7 '-carboxyl-1,1 '-spiro indan (500mg, 1.12mmol), valerian ammonia alcohol (360mg, 3.50mmol), HOBt (380mg, 2.48mmol) and DCC (664mg, 3.22mmol).The frozen water cooling adds the THF (60mL) that heavily steams down, finishes nature and rises to the stirring at room reaction, has a large amount of white precipitates to generate in the system.TLC follows the tracks of reaction, until transforming fully.Add 10g silica gel to system, the rotary evaporation precipitation, the dry method upper prop carries out silica gel column chromatography with petrol ether/ethyl acetate mixed solvent (2: 1) as eluent, obtains compound (S
a, S)-7 '-diphenylphosphino-[1,1 ']-spiro indan-7-[N-(1-methylol-2-methyl-propyl)]-methane amide (600mg, 100%).Product is a thick liquid, puts curing for a long time.[α]
20 D-193.6(c 0.5，CH
2Cl
2)；
1H NMR(400MHz，CDCl
3)δ7.37-6.93(m，16H，Ar-H)，4.80(d，J＝6.8Hz，1H，NH)，3.67(s，1H，OH)，3.35-3.32(m，1H，CH)，3.21-2.88(m，6H，CH
2)，2.88-2.70(m，1H，CH
2)，2.63-2.27(m，3H，CH
2)，1.60-1.51(m，1H，CH)，0.67(d，J＝6.8Hz，3H，CH
3)，0.59(d，J＝6.4Hz，3H，CH
3)；
31P NMR(161MHz，CDCl
3)δ-20.0(s)；
13C NMR(100MHz，CDCl
3)δ170.8，156.0，155.7，149.4，146.4，145.4，140.2，137.5，137.2，135.5，134.2，133.7，133.0，132.7，132.5，129.5，128.6，128.3，127.1，126.6，126.0，63.2，60.8，42.9，40.5，34.2，31.2，28.2，25.2，20.2，19.2；MS(ESI)m/z 532(M-1，44)；Anal.calcd for C
35H
36NO
2P：C 78.77，H 6.80，N 2.62；Found：C 76.67，H 6.69，N 2.89。
Embodiment 15:(R
a, S)-7 '-diphenylphosphino-[1,1 '] spiro indan-7-[N-(1-methylol-2-methyl-propyl)]-preparation of methane amide
With (R)-7-diphenylphosphino-7 '-carboxyl-1,1 '-spiro indan and valerian ammonia alcohol are feedstock production, method is identical with embodiment 14.Product is a heavy-gravity oily matter, puts curing for a long time, yield: 100%.[α]
20 D+178.2(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.38-7.12(m，13H，Ar-H)，7.00(d，J＝6.9Hz，1H，Ar-H)，6.92-6.87(m，2H，Ar-H)，4.55(d，J＝9.0Hz，1H，NH)，3.40-3.22(m，1H，CH
2)，3.22-2.62(m，8H，CH
2)，2.42-2.26(m，2H，CH
2)，1.46-1.34(m，1H，CH)，0.77(d，J＝6.6Hz，3H，CH
3)，0.70(d，J＝6.6Hz，3H，CH
3)；
1P NMR(121MHz，CDCl
3)δ-20.8(s)；
13C NMR(75MHz，CDCl
3)δ170.3，156.7，149.8，146.6，145.9，140.3，137.3，137.1，135.7，135.4，133.7，133.1，132.5，132.2，129.9，128.8，128.7，128.3，127.9，127.1，126.6，126.1，63.5，63.2，57.4，43.1，43.0，40.5，34.2，31.4，31.2，28.9，25.1，19.8，19.3；HRMS(FAB)calcd for C
35H
37NO
2P：534.2556；Found 534.2555。
Embodiment 16:(S
a, S)-7 '-diphenylphosphino-[1,1 '] spiro indan-7-[N-(1-methylol-2-phenyl)]-preparation of methane amide
With (S)-7-diphenylphosphino-7 '-carboxyl-1,1 '-spiro indan and benzene glycinol are feedstock production, method is identical with embodiment 14.Product is a heavy-gravity oily matter, puts curing for a long time, yield 87%.[α]
20 D-169.2(c 0.5，CH
2Cl
2)；
1H NMR(400MHz，CDCl
3)δ7.36-6.84(m，21H，Ar-H)，5.17(d，J＝4.8Hz，1H，NH)，4.27(s，1H，OH)，3.65-3.60(m，1H，CH)，3.46-3.37(m，2H，CH
2)，3.11-2.88(m，4H，CH
2)，2.85-2.80(m，1H，CH
2)，2.57-2.49(m，1H，CH
2)，2.33-2.24(m，2H，CH
2)；
31P NMR(161MHz，CDCl
3)δ-17.7(s)；
13C NMR(100MHz，CDCl
3)δ170.6，155.4，148.9，146.5，139.8，138.7，136.7，134.9，134.7，134.0，133.4，133.0，132.8，132.5，129.2，128.9，128.4，128.2，127.9，127.7，127.2，127.0，126.9，126.0，66.5，63.2，58.4，42.3，40.7，31.3，31.2；MS(ESI)m/z 566(M-1，100)；Anal.calcd for C
38H
34NO
2P：C 80.40，H6.04，N 2.47；Found：C 79.17，H 6.09，N 2.50。
Embodiment 17:(S
a, S)-7 '-diphenylphosphino-[1,1 '] spiro indan-7-[N-(1-methylol-2-benzyl)]-preparation of methane amide
With (S)-7-diphenylphosphino-7 '-carboxyl-1,1 '-spiro indan and phenylalaninol are feedstock production, method is identical with embodiment 14.Product is a white solid, yield: 95%.Mp 178-180℃；[α]
20 D-242.2(c 0.5，CH
2Cl
2)；
1H NMR(400MHz，CDCl
3)δ7.36-6.80(m，21H，Ar-H)，4.68(br，1H，NH)，3.21-2.59(m，8H，CH
2and CH)，2.69-2.61(m，1H，CH
2)，2.39-2.18(m，4H，CH
2)；
31P NMR(161MHz，CDCl
3)δ-20.8(s)；
13C NMR(100MHz，CDCl
3)δ170.3，156.0，155.8，149.2，146.2，145.6，140.1，138.7，137.3，137.1，135.5，134.1，133.6，133.2，133.0，132.7，132.5，129.6，129.4，128.7，128.3，127.8，127.8，127.1，126.7，126.6，126.1，63.6，63.2，55.4，42.6，40.7，35.9，31.4，31.2；HRMS(FAB)calcd for C
39H
35NO
2P：580.2400；Found580.2385。
Embodiment 18:(S
a, S)-7 '-two (4-p-methoxy-phenyl) phosphino--[1,1 '] spiro indan-7-[N-(1-methylol-2-benzyl)]-preparation of methane amide
With (S)-7-two (4-p-methoxy-phenyl) phosphino--7 '-carboxyl-1,1 '-spiro indan and phenylalaninol are feedstock production, method is identical with embodiment 14.Product is a white solid, yield: 91%.
1H NMR(300MHz，CDCl
3)δ7.36-6.99(m，10H，Ar-H)，6.82(d，J＝11.4Hz，2H，Ar-H)，6.67(d，J＝7.8Hz，3H，Ar-H)，6.52(d，J＝6.9Hz，2H，Ar-H)，4.23(d，J＝6.6Hz，1H，CH)，3.22-2.80(m，9H，CH
2)，2.44-2.26(m，5H，CH
2)，2.16(s，6H，CH
3)，2.15(s，6H，CH
3)；
31P NMR(121MHz，CDCl
3)δ-20.8(s)；
13C NMR(75MHz，CDCl
3)δ170.8，156.0，155.7，149.7，146.3，145.7，145.5，140.5，140.3，139.0，137.9，137.8，137.6，136.8，136.6，134.2，133.8，133.5，131.7，130.8，129.8，129.6，129.3，128.7，127.8，127.4，126.7，126.5，126.0，125.1，64.1，63.2，56.4，43.3，43.2，41.2，41.0，35.5，34.0，31.4，31.2，21.5，21.4；HRMS(EI)calcd for C
43H
44NO
2P：637.3109；Found 637.3105。
Embodiment 19:(S
a, S)-7 '-two (3, the 5-3,5-dimethylphenyl) phosphino--[1,1 '] spiro indan-7-[N-(1-methylol-2-benzyl)]-preparation of methane amide
With (S)-7-two (3, the 5-3,5-dimethylphenyl) phosphino--7 '-carboxyl-1,1 '-spiro indan and phenylalaninol are feedstock production, method is identical with embodiment 14.Product is a white solid, yield: 91%.
1H NMR(300MHz，CDCl
3)δ7.36-6.99(m，10H，Ar-H)，6.82(d，J＝11.4Hz，2H，Ar-H)，6.67(d，J＝7.8Hz，3H，Ar-H)，6.52(d，J＝6.9Hz，2H，Ar-H)，4.23(d，J＝6.6Hz，1H，CH)，3.22-2.80(m，9H，CH
2)，2.44-2.26(m，5H，CH
2)，2.16(s，6H，CH
3)，2.15(s，6H，CH
3)；
31P NMR(121MHz，CDCl
3)δ-20.8(s)；
13C NMR(75MHz，CDCl
3)δ170.8，156.0，155.7，149.7，146.3，145.7，145.5，140.5，140.3，139.0，137.9，137.8，137.6，136.8，136.6，134.2，133.8，133.5，131.7，130.8，129.8，129.6，129.3，128.7，127.8，127.4，126.7，126.5，126.0，125.1，64.1，63.2，56.4，43.3，43.2，41.2，41.0，35.5，34.0，31.4，31.2，21.5，21.4；HRMS(EI)calcd for C
43H
44NO
2P：637.3109；Found 637.3105。
Embodiment 20:(S
a, S)-2-[(7 '-diphenylphosphino)-1,1 ' spiro indan-7-]-4-sec.-propyl-4, the preparation of 5-dihydro-oxazole
In the 100mL Schlenk reaction flask of induction stirring is housed, be weighed into (S
a, S)-7 '-diphenylphosphino-[1,1 ']-spiro indan-7-[N-(1-methylol-2-methyl-propyl)]-methane amide (600mg, 1.13mmol) and DMAP (5mg 0.041mmol), is replaced as nitrogen atmosphere on the vacuum line.Add 70mL and heavily steam the CH of the back degassing
2Cl
2And stirring makes evenly.The ice-water bath cooling adds 0.34mL Et down successively
3N and MsCl (170 μ L) keep this temperature stirring reaction 30min, add 1.45mL Et
3N makes system rise to stirred overnight at room temperature naturally.TLC follows the tracks of reaction, until transforming fully.Add 10g silica gel cancellation reaction in system, direct dry method upper prop adds 2% Et with petrol ether/ethyl acetate mixed solvent (10: 1) behind the vacuum precipitation
3N carries out column chromatography as eluent, obtains compound (S
a, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-sec.-propyl-4,5-dihydro-oxazole (400mg, 69%).Product is a white foam shape solid.Mp 40-45℃；[α]
20 D-243.2(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.54(d，J＝6.6Hz，1H，Ar-H)，7.26-6.89(m，14H，Ar-H)，6.76-6.72(m，1H，Ar-H)，3.46-3.37(m，2H，CH
2)，3.17-3.09(m，1H，CH)，2.98-2.82(m，3H，CH
2)，2.72-2.52(m，2H，CH
2)，2.18-2.11(m，1H，CH
2)，2.10-2.01(m，1H，CH
2)，1.80-1.74(m，1H，CH
2)，1.36-1.19(m，1H，CH)，0.80(d，J＝6.6Hz，3H，CH
3)，0.67(d，J＝6.6Hz，3H，CH
3)；
1P NMR(121MHz，CDCl
3)δ-20.3(s)；
13C NMR(75MHz，CDCl
3)δ164.3，154.7，154.3，149.2，145.1，144.9，144.8，138.8，138.6，138.5，138.3，134.2，133.9，133.5，132.7，132.4，132.0，128.8，128.4，128.1，128.0，126.9，126.8，126.0，125.1，72.3，68.6，63.5，40.3，38.6，32.9，31.2，30.8，29.9，19.4，18.4；HRMS(FAB)calcd for C
35H
34NOP：516.2451；Found516.2454。
Embodiment 21:(R
a, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-sec.-propyl-4, the preparation of 5-dihydro-oxazole
With (R
a, S)-7 '-diphenylphosphino-[1,1 ']-spiro indan-7-[N-(1-methylol-2-methyl-propyl)]-methane amide is a feedstock production, method is identical with embodiment 20.Product is a thick liquid, puts curing for a long time, yield: 89%.[α]
20 D+193.4(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.40(d，J＝7.5Hz，1H，Ar-H)，7.35-6.94(m，14，Ar-H)，6.89-6.82(m，1H，Ar-H)，3.79(t，J＝7.5Hz，1H，CH)；3.22-2.75(m，7H，CH
2)，2.25-2.12(m，3H，CH
2)，1.30-1.18(m，1H，CH)，0.88(d，J＝6.3Hz，3H，CH
3)，0.63(d，J＝6.6Hz，3H，CH
3)；
31P NMR(121MHz，CDCl
3)δ-21.1(s)；
13C NMR(75MHz，CDCl
3)δ162.9，155.7，155.3，150.7，145.3，145.2，145.1，139.4，139.2，138.1，137.9，134.4，134.1，133.8，133.7，133.5，131.9，131.7，128.8，128.3，128.2，128.1，126.9，126.7，126.4，125.4，125.0，73.7，70.1，63.6，41.5，38.2，33.1，31.4，30.9，20.1，19.2；MS(ESI)m/z 516(M+1
+，100)；Anal.calcd for C
35H
34NOP：C 81.53，H 6.65；Found：C 81.42.H 6.50。
Embodiment 22:(S
a, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-phenyl-4, the preparation of 5-dihydro-oxazole
With (S
a, S)-7 '-diphenylphosphino-[1,1 ']-spiro indan-7-[N-(1-methylol-2-phenyl)]-methane amide is a feedstock production, method is identical with embodiment 20.Product is a white foam shape solid, yield: 69%.Mp 159-160℃；[α]
20 D-238.0(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.77(d，J＝7.5Hz，1H，Ar-H)，7.40-6.85(m，20H，Ar-H)，4.78(dd，J＝10.2and 6.9Hz，1H，CH)，3.67(dd，J＝8.1and 7.2Hz，1H，CH
2)，3.37(t，J＝8.4Hz，1H，CH
2)，3.12-2.94(m，3H，CH
2)，2.86-2.78(m，1H，CH
2)，2.65(dd，J＝22.2and 10.5Hz，1H，CH
2)，2.29-1.95(m，3H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-20.6(s)；
13C NMR(75MHz，CDCl
3)δ165.6，154.9，154.6，149.6，145.1，144.7，144.6，142.7，138.8，138.6，137.9，137.7，134.2，134.1，133.9，133.8，133.6，133.5，132.4，129.2，128.5，128.2，128.1，128.0，127.9，127.2，126.7，126.6，126.5，73.8，69.1，63.6，40.7，40.6，38.4，31.0，30.7；MS(EI)m/z 549(M，54)，402(100)；Anal.calcd for C
38H
32NOP：C 83.04，H 5.87，N 2.55；Found：C82.92，H 5.81，N 2.53。
Embodiment 23:(S
a, S)-2-[(7 '-diphenylphosphino)-[1,1 '] spiro indan-7-]-4-benzyl-4, the preparation of 5-dihydro-oxazole
With (S
a, S)-7 '-diphenylphosphino-[1,1 '-spiro indan-7-[N-(1-methylol-2-benzyl)]-methane amide is a feedstock production, method is identical with embodiment 20.Product is a white foam shape solid, yield: 75%.Mp 49-51℃；[α]
20 D-227.0(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.61(d，J＝7.2Hz，1H，Ar-H)，7.37-6.83(m，20H，Ar-H)，4.11-4.01(m，1H，CH)，3.50(dd，J＝8.4and 6.6Hz，1H，CH
2)，3.25(t，J＝9.0Hz，1H，CH
2)，3.05-2.92(m，3H，CH
2)，2.82-2.68(m，3H，CH
2)，2.26-1.89(m，4H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-20.9(s)；
13CNMR(75MHz，CDCl
3)δ164.3，155.3，155.0，149.7，145.3，145.0，139.0，138.8，134.3，134.0，133.8，132.5，132.3，129.4，128.9，128.7，128.3，127.2，126.8，126.7，126.5，125.7，125.3，70.9，67.5，63.7，41.3，40.7，38.5，31.2，30.9；HRMS(FAB)calcd for C
39H
35NOP：564.2451；Found564.2463。
Embodiment 24:(S
a, S)-2-[(7 '-two (4-p-methoxy-phenyl) phosphino-)-1,1 '-spiro indan-7-]-4-benzyl-4, the preparation of 5-dihydro-oxazole
With (S
a, S)-7 '-two (4-p-methoxy-phenyl) phosphino--[1,1 ']-spiro indan-7-[N-(1-methylol-2-benzyl)]-methane amide is a feedstock production, method is identical with embodiment 20.Product is a white foam shape solid, yield: 76%.[α]
20 D-221.6(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.62(d，J＝7.2Hz，1H，Ar-H)，7.36-6.74(m，18H，Ar-H)，4.09-3.99(m，1H，CH
2)，3.77(s，3H，CH
3)，3.76(s，3H，CH
3)，3.50(dd，J＝8.4 and 6.6Hz，1H，CH
2)，3.21(t，J＝9.0Hz，1H，CH)3.03-2.90(m，3H，CH
2)，2.79-2.66(m，3H，CH
3)，2.24-2.17(m，1H，CH
2)，2.06-1.98(m，2H，CH
2)，1.92-1.81(m，1H，CH
2)；
31P NMR(121MHz，CDCl
3)δ-24.2(s)；
13C NMR(100MHz，CDCl
3)δ164.4，160.9，159.9，159.8，159.7，159.2，154.4，154.2，149.5，145.2，144.8，138.8，135.5，135.3，133.8，133.6，133.1，129.7，129.5，129.3，128.7，128.6，127.0，126.7，126.5，125.9，125.0，114.0，70.9，67.3，63.6，55.3，41.2，40.1，38.5，31.1，30.8；HRMS(EI)calcd for C
41H
38NO
3P：623.2597；Found 623.2589。
Embodiment 25:(S
a, S)-2-[(7 '-two (3, the 5-3,5-dimethylphenyl) phosphino-)-1,1 '-spiro indan-7-]-4-benzyl-4, the preparation of 5-dihydro-oxazole
With (S
a, S)-7 '-two (3, the 5-3,5-dimethylphenyl) phosphino--[1,1 '] spiro indan-7-[N-(1-methylol-2-benzyl)]-methane amide is a feedstock production, method is identical with embodiment 20.Product is a colourless liquid, puts curing for a long time, yield: 70%.[α]
24 D-196.8(c 0.51，CH
2Cl
2)；
1HNMR(300MHz，CDCl
3)δ7.60(d，J＝7.5Hz，1H，Ar-H)，7.36-6.86(m，12H，Ar-H)，6.77(d，J＝7.8Hz，2H，Ar-H)，6.60(d，J＝7.5Hz，2H，Ar-H)；4.14-4.04(m，1H，CH
2)，3.49(dd，J＝8.4and 6.6Hz，1H，CH
2)，3.32(t，J＝8.8Hz，1H，CH)，3.05-2.91(m，3H，CH
2)，2.82-2.63(m，3H，CH
2)，2.20(s，6H，CH
3)，2.18(s，6H，CH
3)，2.10-1.86(m，4H，CH
2)；
31PNMR(121MHz，CDCl
3)δ-20.6(s)；
13C NMR(100MHz，CDCl
3)δ164.1，155.2，155.0，149.7，145.3，144.7，138.9，137.4，137.2，133.6，131.9，131.6，130.0，129.9，129.3，128.8，127.0，126.6，126.4，124.9，70.8，67.4，63.7，41.2，40.4，38.6，31.2，30.8，21.5；HRMS(EI)calcd forC
43H
42NOP：619.3004；Found 619.2978。
Embodiment 26:[(S
a, S)-Ph-SIPHOX-
iPr-Ir (COD)] preparation of BARF
In glove box, take by weighing part (S
a, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-sec.-propyl-4, (60mg is 0.12mmol) with [Ir (COD) Cl] for the 5-dihydro-oxazole
2(60mg 0.09mmol) in 20mL Schlenk reaction flask, takes out the back and adds the new CH that steams with syringe
2Cl
2(3mL), 50 ℃ of heated and stirred of oil bath reaction 18h, sampling TLC or
31P NMR monitoring reaction situation stops heating after the complete complexing of part, allow system reduce to room temperature naturally.Add H under the vigorous stirring
2O (1mL) and NaBARF (170mg) finish and continue reaction 30min, add CH
2Cl
2(20mL) diluted system, separatory, organic phase anhydrous Na
2SO
4Drying, the rotary evaporation precipitation, the resistates column chromatography can obtain [(S
a, S)-Ph-SIPHOX-
iPr-Ir (COD)] BARF (160mg, 80%).Product is an orange spumescence solid.Mp 170-172℃；[α]
15 D+186.7(c 0.58，CH
2Cl
2)；
1HNMR(300MHz，CDCl
3)δ8.19(d，J＝6.9Hz，1H)，7.72-7.20(m，26H)，6.64(s，1H)，4.71(s，1H)，4.25-4.20(m，1H)，3.88(s，2H)，3.55-3.51(m，1H)，3.02-2.62(m，5H)，2.51-1.82(m，7H)，1.62-1.17(m，6H)，0.87(dd，J＝21.6 and 6.3Hz，6H)，0.49-0.37(m，1H)；
31P NMR(121MHz，CDCl
3)δ15.3(s)；
13C NMR(100MHz，CDCl
3)δ173.3，162.7，162.2，161.7，161.2，148.9，148.8，148.1，148.0，146.6，144.4，135.0，133.5，133.4，133.2，132.7，132.4，130.9，130.7，129.7，129.6，129.3，129.0，128.9，128.7，128.6，128.4，128.3，127.8，127.4，127.3，127.1，126.1，124.6，123.4，121.1，120.7，117.1，75.7，72.2，71.7，70.8，68.5，63.0，41.4，34.4，32.2，31.3，31.0，30.4，30.0，29.5，19.2，14.5，1.3；MS(ESI)m/z 816(M
+，40)，706(100)；Anal.calcd for C
75H
58BF
24IrNOP：C 53.64，H 3.48，N 0.83；Found：C 53.64，H 3.34，N 0.80。
Embodiment 27:[(R
a, S)-Ph-SIPHOX-
iPr-Ir (COD)] preparation of BARF
With (R, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-sec.-propyl-4,5-dihydro-oxazole and [Ir (COD) Cl]
2Be feedstock production, method is identical with embodiment 26.Product is an orange spumescence solid, yield: 80%.Mp 177-179℃；[α]
15 D-52.2(c 0.45，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ7.72(s，8H)，7.53-7.23(m，18H)，7.08-7.02(m，2H)，4.70-4.63(m，1H)，4.56-4.44(m，2H)，3.94-3.84(m，1H)，3.62-3.55(m，1H)，3.40-3.55(m，1H)，2.99-2.82(m，2H)，2.61-2.49(m，1H)；2.37-2.04(m，5H)，1.98-1.81(m，2H)，1.62(d，J＝6.6Hz，3H)，0.46(d，J＝6.6Hz，3H)；
31P NMR(121MHz，CDCl
3)δ14.2(s)；
13C NMR(100MHz，CDCl
3)δ173.7，162.7，162.2，161.7，161.2，149.7，149.6，147.4，147.2，144.0，137.3，137.2，135.0，134.6，134.5，132.6，132.1，131.1，129.7，129.5，129.3，129.1，129.0，128.7，128.6，128.4，128.3，127.5，126.9，126.5，126.1，123.4，120.7，117.6，85.0，84.8，83.6，83.5，73.4，72.2，71.7，65，6，63.9，40.0，36.1，33.0，32.3，30.6，30.0，29.6，28.6，24.7，17.2；MS(ESI)m/z 816(M
+，20)，706(100)；Anal.calcdfor C
75H
58BF
24IrNOP：C 53.64，H 3.48，N 0.83；Found：C 53.64，H 3.34，N 0.80。
Embodiment 28:[(S
a, S)-and Ph-SIPHOX-Ph-Ir (COD)] preparation of BARF
With (S
a, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-phenyl-4,5-dihydro-oxazole and [Ir (COD) Cl]
2Be feedstock production, method is identical with embodiment 26.Product is an orange spumescence solid, yield: 85%.Mp 166-167℃；[α]
15 D+191.7(c0.54，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ8.06(d，J＝7.2Hz，1H，)，7.77-7.26(m，30H)，6.82-6.70(m，2H)，4.46-4.31(m，2H)，3.90-3.70(m，2H)，3.65-3.50(m，1H)，3.40(t，J＝9.3Hz，1H)，2.96-2.73(m，4H)，2.34-2.01(m，5H)，1.71-1.54(m，1H)，1.37-1.15(m，5H)，0.97-0.76(m，2H)；
31P NMR(121MHz，CDCl
3)δ14.5(s)；
13C NMR(100MHz，CDCl
3)δ171.8，162.7，162.2，161.7，161.2，148.6，148.5，148.4，148.3，146.4，144.4，138.0，135.9，135.0，133.8，133.7，132.9，132.8，132.4，132.3，130.9，130.7，130.3，130.1，129.7，129.6，129.3，129.0，128.8，128.7，128.6，128.5，128.4，128.0，127.6，127.3，126.9，126.1，125.9，123.4，121.3，120.7，117.7，79.7，78.6，72.5，72.3，70.5，69.8，69.1，63.3，41.6，34.3，31.7，30.9，30.4，29.8，29.1；MS(ESI)m/z 850(M
+，68)，740(100)；Anal.calcd for C
78H
56BF
24IrNOP：C 54.68，H 3.29，N 0.82；Found：C54.70，H 3.10，N 0.85。
Embodiment 29:[(S
a, S)-and Ph-SIPHOX-Bn-Ir (COD)] preparation of BARF
With (S
a, S)-2-[(7 '-diphenylphosphino)-1,1 '-spiro indan-7-]-4-benzyl-4,5-dihydro-oxazole and [Ir (COD) Cl]
2Be feedstock production, method is identical with embodiment 26.Product is an orange spumescence solid, yield: 90%.Mp 178-179℃；[α]
15 D+168.6(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ8.11(d，J＝6.9Hz，1H)，7.73-7.51(m，16H)，7.39-7.07(m，8H)，6.71(s，2H)，4.91-4.86(m，1H)，4.20-4.10(m，2H)，3.91-3.85(m，1H)，3.79-3.69(m，1H)，3.17-3.64(m，6H)，2.63-2.40(m，1H)，2.32-2.04(m，4H)，1.98-1.86(m，1H)，1.60-1.26(m，4H)，0.90-0.76(m，4H).
31P NMR(121MHz，CDCl
3)δ14.9(s)；
13CNMR(100MHz，CDCl
3)δ173.1，162.7，162.2，161.7，161.2，148.7，148.2，146.6，144.5，135.8，135.7，135.1，134.4，133.6，133.5，132.9，132.8，132.4，132.3，130.8，130.7，129.8，129.6，128.9，128.7，128.5，128.4，128.1，127.6，127.3，127.2，126.8，126.2，125.3，123.5，121.1，120.7，117.7，76.6，75.2，71.6，69.2，67.1，63.2，41.5，41.0，34.5，32.1，30.9，30.4，30.2，29.4；MS(ESI)m/z 864(M
+，68)，754(100)；Anal.calcdfor C
79H
58BF
24IrNOP：C 54.93，H 3.38，N 0.81；Found：C 54.95，H 3.19，N 0.87。
Embodiment 30:[S
a, S)-and An-SIPHOX-Bn-Ir (COD)] preparation of BARF
With (S
a, S)-2-[(7 '-two (4-p-methoxy-phenyl) phosphino-)-1,1 '-spiro indan-7-]-4-benzyl-4,5-dihydro-oxazole and [Ir (COD) Cl]
2Be feedstock production, method is identical with embodiment 26.Product is an orange spumescence solid, yield: 95%.Mp 83-84℃；[α]
15 D+136.6(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ8.05-8.66(m，31H)，4.87(s，1H)；4.17-4.12(m，1H)，3.84(d，J＝11.7Hz，6H)，3.69-3.65(m，1H)，3.20-2.63(m，6H)，2.49-2.37(m，1H)，2.33-2.02(m，3H)，1.92-1.59(m，3H)，1.40-1.16(m，3H)，1.14-0.79(m，4H)，0.31-0.20(m，1H)；
31P NMR(121MHz，CDCl
3)δ12.1(s)；
13C NMR(75MHz，CDCl
3)δ172.5，172.4，162.8，162.7，162.0，161.3，160.7，148.3，148.2，147.9，147.8，146.1，144.7，137.3，137.1，135.1，134.8，134.2，131.9，130.2，130.0，129.5，129.4，129.3，128.6，128.1，127.9，127.7，127.0，126.4，125.3，123.5，122.8，121.0，119.1，118.5，117.5，117.4，115.1，114.9，114.2，114.0，74.8，70.9，70.6，70.4，69.0，66.9，63.0，55.5，55.4，41.4，40.7，34.5，31.7，30.9，30.6，30.5，29.9，29.2；MS(ESI)m/z 924(M
+，40)，814(100)；Anal.calcdfor C
81H
62BF
24IrNO
3P：C 54.43，H 3.50，N 0.78；Found：C 54.43，H 3.46，N 1.00。
Embodiment 31:[(S
a, S)-and Xyl-SIPHOX-Bn-Ir (COD)] preparation of BARF
With (S
a, S)-2-[(7 '-two (3, the 5-3,5-dimethylphenyl) phosphino-)-1,1 '-spiro indan-7-]-4-benzyl-4,5-dihydro-oxazole and [Ir (COD) Cl]
2Be feedstock production, method is identical with embodiment 26.Product is an orange spumescence solid, yield: 92%.Mp 177-179℃；[α]
15 D+174.6(c 0.5，CH
2Cl
2)；
1H NMR(300MHz，CDCl
3)δ8.07(d，J＝7.2Hz，1H)，7.72(s，8H)，7.59-7.51(m，7H)，7.34-7.06(m，13H)，4.80(s，1H)，4.18-4.12(m，2H)，3.80-3.67(m，2H)，3.20-3.16(m，1H)，3.01-2.65(m，6H)，2.52-2.03(m，15H)，1.63-1.52(m，1H)，1.39-1.25(m，4H)，1.04-0.76(m，4H)，0.67-0.57(m，1H)；
31P NMR(121MHz，CDCl
3)δ14.8(s)；
13C NMR(100MHz，CDCl
3)δ172.8，162.8，162.3，161.8，161.3，148.5，148.4，148.0，146.5，144.8，139.5，138.4，138.3，135.1，134.7，134.3，132.5，132.3，131.8，131.6，131.5，130.0，129.6，129.4，129.1，128.9，128.8，128.4，128.1，127.6，127.3，127.1，126.8，126.2，125.4，123.5，121.2，120.8，117.7，76.0，75.2，71.1，70.3，70.2，70.1，69.7，67.4，63.3，41.5，41.1，34.2，31.7，30.8，30.6，30.0，29.8，21.8，21.4；MS(ESI)m/z 920(M
+，10)，810(100)；Anal.calcd for C
83H
66BF
24IrNOP：C55.90，H 3.73，N 0.79；Found：C 56.14，H 3.56，N 0.98。
The catalytic hydrogenation of embodiment 32:N-aryl ketones imines
(with [S
a, S)-Xyl-SIPHOX-Bn-Ir (COD)] BARF catalytic hydrogenation N-phenyl (1-phenyl ethidine) amine is example)
In glove box, take by weighing catalyzer [(S
a, S)-and Xyl-SIPHOX-Bn-Ir (COD)] (39mg 2mmol) in the Schlenk reaction tubes that stirrer is housed, seals standby for BARF (3.7mg, 2 μ mol) and N-phenyl (1-phenyl ethidine) amine.Take out the back and add t-butyl methyl ether (1mol) with syringe, the degassing is three times on biexhaust pipe, with hydrogen balloon system is replaced as H for the last time
2Atmosphere.After keeping 10 ℃ of reaction 20hrs, stop to stir, releasing hydrogen gas revolves reaction system after inspissation contracts underpressure distillation (100 ℃/5Pa) obtain normal hydrogenated products N-phenyl (1-phenylethyl) amine are colourless limpid liquid.GC analyzes its transformation efficiency, and chirality HPLC analyzes its ee value.
Gained catalytic hydrogenation experimental result 1 (the imines R that sees the following form
4R
5C=NR
3In: with R
4=Ph, 4-MePh, 4-MeOPh, 4-ClPh, 4-BrPh, 3-ClPh, 3-BrPh, 3,4-diMePh; R
5=CH
3R
3=Ph, 4-ClPh, 4-BrPh, 4-MePh, 3-MePh, 3-BrPh are example).
Table 1: the experimental result of imines catalytic hydrogenation
| R | R′ | Transformation efficiency | ee(％) b | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 | H 4-MeO 4-Me 4-Cl 4-Br 3-Cl 3-Br 3，4-diMe H H H H H | H H H H H H H H 4-Me 4-Cl 4-Br 3-Me 3-Br | 100 100 100 100 100 100 100 100 100 100 100 100 100 | 93(R) 94(-) 94(-) 90(-) 91(R) 93(-) 92(-) 94(-) 93(-) 97(-) 96(+) 91(-) 94(-) |
Claims (7)
1. novel volution phosphine-oxazoline part is characterized in that having the compound of following structural formula:
Wherein: R
1Be C
1～C
6Alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
6Alkyl,-oxyl and halo alkyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl, benzyl; Described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl; Described-oxyl is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy; R
2Be C
1～C
6Alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
6Alkyl,-oxyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl, 2-furyl, benzyl.
2. according to the described compound of claim 1, it is characterized in that it is dextrorotation volution phosphine-oxazoline part-(R
a, R)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan base-7-]-4-replacement-4,5-dihydro-oxazole or (S
a, R)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan-7-]-4-replacement-4,5-dihydro-oxazole, left-handed volution phosphine-oxazoline part-(S
a, S)-2-[(7 '-diarylphosphino)-1,1 '-spiro indan-7-]-4-replacement-4,5-dihydro-oxazole or (R
a, S)-2-[[(7 '-diarylphosphino)-1,1 '-spiro indan-7-]-4-replacement-4, the 5-dihydro-oxazole.
3. the preparation method of compound according to claim 1 is characterized in that it is through following step preparation, by optical purity 1,1 '-spiro indan-7,7 '-diphenol sets out, reaction makes volution phosphine-oxazoline parts through 7 steps:
4. according to the preparation method of the described compound of claim 3, it is characterized in that with optically pure 1,1 '-spiro indan-7,7 '-diphenol is a starting raw material, through becoming ester with trifluoromethanesulfanhydride anhydride, the palladium catalytic coupling, trichlorosilane reduction generation important intermediate 7-diarylphosphino-7 '-trifluoro-methanesulfonyl oxy-1,1 '-spiro indan, this intermediate carries out the catalytic esterification of palladium, alkaline condition is hydrolyzed into acid, and then becomes acid amides alcohol with the chiral amino of 2 replacements is ethanol condensed, and last cyclisation obtains volution phosphine-oxazoline parts.
5. by the set out a kind of novel iridium complex of preparation of compound according to claim 1, it is characterized in that having the compound of following structural formula:
R
1Be C
1～C
6Alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
6Alkyl,-oxyl and halo alkyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl, benzyl; Described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl; Described-oxyl is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy; R
2Be C
1～C
6Alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
6Alkyl,-oxyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl, 2-furyl, benzyl; X is a hexafluoro-phosphate radical, hexafluoro tellurate radical, tetrafluoroborate, tetraphenyl borate, four-(3,5-two trifluoromethyls) borates.
6. as the preparation method of compound as described in the claim 5, it is characterized in that it is through following step preparation, set out and [Ir (COD) Cl] by compound according to claim 1
2Reaction makes the iridium complex of chiral spiro phosphine-oxazoline parts:
7. as application of compound as described in the claim 5, it is characterized in that described ionic type iridium complex compound is used to contain the catalytic hydrogenation of the latent chipal compounds of carbon-to-nitrogen double bon as catalyzer in solvent; Described solvent is chloroparaffin, benzene, toluene or ether solvent; Catalyst levels is 1%～0.01%, and temperature of reaction is 0～40 ℃, and the reaction times is 6 hours～48 hours;
Wherein:
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