CN101555259B - Phosphine oxazoline ligand of spiral ring skeleton, a synthetic method thereof and applications in asymmetric hydrogenation of various types of imine coumpounds and various types of non-functionalized - Google Patents

Phosphine oxazoline ligand of spiral ring skeleton, a synthetic method thereof and applications in asymmetric hydrogenation of various types of imine coumpounds and various types of non-functionalized Download PDF

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CN101555259B
CN101555259B CN2009100513143A CN200910051314A CN101555259B CN 101555259 B CN101555259 B CN 101555259B CN 2009100513143 A CN2009100513143 A CN 2009100513143A CN 200910051314 A CN200910051314 A CN 200910051314A CN 101555259 B CN101555259 B CN 101555259B
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CN101555259A (en
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丁奎岭
韩召斌
王正
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a phosphine oxazoline ligand of a spiral ring skeleton, a synthetic method thereof and applications in asymmetric hydrogenation of various types of imine coumpounds and various types of non-functionalized olefin thereof. The synthetic method is simple and convenient and direct; and the spiral ring skeleton obtained from spiro-diketone has optical pure chiral ligand with different absolute configurations. The phosphine oxazoline ligand of the spiral ring skeleton is a compound with wide application, for example, can be applied in asymmetric hydrogenation as chiral ligand. Especially, the ionic iridium complex of the phosphine oxazoline ligand obtains excellent reactional activity and enantioselectivity in the asymmetric hydrogenation of imine and olefin.

Description

Volution skeleton Lin oxazoline part, compound method and the application in asymmetric hydrogenation thereof
Technical field
The present invention relates to the preparation method and use of one type of New-type spiro skeleton Lin oxazoline part and such part.Such part can be used for preparing the positively charged ion iridium complex.These iridium complexs react at asymmetric catalytic hydrogenation, especially in the asymmetric hydrogenation of polytype imines and non-functionalization alkene, good application are arranged all.
Background technology
The asymmetric catalytic hydrogenation reaction is one of important method in the asymmetric synthesis, is widely used in chemical industry process [Ohkuma, T.; Kitamura, M.; Noryori, R. (1999) Asymmetric Hydrogenation.In:Ojiama, I. (ed) Catalytic Asymmetric Synthesis. (2nd Ed.) .Wily-VCH:NewYork (Englinsh) 2000]; [The Handbook of Homogeneous Hydrogenation; Vol.I-III (Eds.:J.G.de Vries, C.J.Elsevier), Wiley-VCH; Weinheim, 2007].And the part of design and exploitation high reactivity and highly selective and catalystsystem thereof are the keys of asymmetric catalytic hydrogenation reaction.In the design of chiral ligand, the selection of chiral ligand skeleton is very important.In recent years, chiral spiro skeleton deutero-part had received some chemists' attention.The chiral ligand of some volution skeletons is synthesized out and is applied in some asymmetric catalysis.[Xie，J.-H.；Zhou，Q.-L.；Acc.Chem.Res.2008，41，581]，[Ding，K.；Han，Z；Wang，Z；Chem.Asian?J.2009，4，32]。Lin oxazoline part is one type of important P, N part, and good application is all arranged in the asymmetric reaction of many metal catalytics.[McManus，H.A.；D.Cusack，D.；Guiry，P.in?Phosphorus?Ligands?in?Asymmetric?Catalysis(Eds：A.
Figure G2009100513143D00011
)，Willy-VCH，Weinheim，2008，p.549]，[Pfaltz，A.；Bell，S.in?Handbook?ofHomogeneous?Hydrogenation(Eds：J.G.de?Vries，C.J.Elsevies)，Wiley-VCH，Weinheim，2007，p.1193]，[Pfaltz，A.；William，J.D.III?Proc.Nat.Acad.Sci.USA2004，101，5723]。2006, Zhou Qilin etc. developed the phosphine oxazoline part (SIPHOX) based on the spiro indan skeleton, and the positively charged ion iridium complex of such part can show outstanding enantioselectivity in the asymmetric hydrogenation of N-aryl ketones imines.[Zhu，S.-F.；Xie，J.-B.；Zhang，Y.-Z.；Li，S.；Zhou，Q.-L.；J.Am.Chem.Soc.2006，128，12886]。Such iridium complex also can show good active and very high enantioselectivity at the α of alpha-substitution in the asymmetric hydrogenation of beta-unsaturated carboxylic acid.[Li，S.；Zhu，S.-F.；Zhang，C.-M.；Song，S.；Zhou，Q.-L.；J.Am.Chem.Soc.2008，130，8584]。The development that patent of the present invention is successful one type of novel volution skeleton De Lin oxazoline part; And this part is applied to obtain high reactive behavior and enantioselectivity in the asymmetric hydrogenation of catalytic polytype group with imine moiety of iridium and non-functionalization alkene.
Summary of the invention
The purpose of this invention is to provide one type of novel volution skeleton Lin oxazoline part and ionic type iridium complex compound thereof.
Another object of the present invention provides the compound method of a kind of above-mentioned part and ionic type iridium complex compound thereof.
The object of the invention also provides the purposes of above-mentioned part and ionic type iridium complex compound thereof, promptly can be used for the asymmetric hydrogenation of the non-functionalization alkene of broad variety group with imine moiety and broad variety.
The structure of part provided by the invention and ionic type iridium complex compound thereof is following:
Figure G2009100513143D00021
Wherein, n=0-3 recommends n=1.
R 1, R 2Be selected from hydrogen, C respectively 1-6Alkyl or R xOr/and R x' substituted-phenyl is recommended R 1=R 2=H.
R 3=C 1-6Alkyl or benzyl.
Ar=phenyl, R xOr/and R x' substituted-phenyl or 2-furyl.
X=hexafluoro-phosphate radical, hexafluoro tellurate radical, tetrafluoroborate, tetraphenyl borate, four-(3,5-two trifluoromethyls) borates.
Described R x, R x' be selected from hydrogen, C respectively 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Perfluoroalkyl, C 5-7Naphthenic base, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl or halogen.
Described C 1-6Alkyl can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl,, sec.-butyl, isobutyl-, isopentyl, cyclopentyl, cyclohexyl or phenyl etc.
Described C 1-4Alkyl, C 1-4Alkoxyl group and C 5-7Naphthenic base be recommended as methyl, methoxyl group, ethyl, oxyethyl group, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl or suberyl etc.
R 1, R 2It can be identical or different group.
This part can be (5S, 4 ' S), (5R, 4 ' S), (5S, 4 ' R) or (5R, the compound of 4 ' R) configurations (wherein 5,4 ' be the numbering of carbon in the ligand structure formula).Its structure is distinguished as follows:
Figure G2009100513143D00031
The present invention also provides the compound method of above-mentioned part, exactly from racemic volution diketone 1 ', with this diketone and two trifluoro-methylsulfonyl aniline (PhNTf 2) reaction generate mono alkenyl triflate 2 ', compound 2 ' through obtaining acid amides alcohol, this acid amides alkylol cpd generation intramolecular cyclization with optically pure amino alcohol and carbon monoxide effect obtain compound 3 ' a pair of diastereomer.Obtain respectively after this a pair of diastereomer separated (5S, 4 ' S) with (5R, 4 ' S) or (5S, 4 ' R) with (5R, the compound 3 of 4 ' R) configurations '.(5S, 4 ' S) or (5R, 4 ' S) or (5S, 4 ' R) or (5R, the compound 3 of 4 ' R) configurations ' with two trifluoro-methylsulfonyl aniline (PhNTf 2) reaction generate (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (5S, the compound 4 of 4 ' R) configurations '.(5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (5S, the compound 4 of 4 ' R) configurations ' with diaryl phosphine hydrogen (Ar 2PH) reaction obtains target ligand, promptly (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (5S, the compound 5 of 4 ' R) configurations '.
Compound 3 in the inventive method ' can be (5S, 4 ' S) or (5R, 4 ' S) or (5S, 4 ' R) or (its structure is following for 5R, 4 ' R) configurations:
Compound 4 in the inventive method ' can be (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (its structure is following for 5S, 4 ' R) configurations:
Figure G2009100513143D00041
OTf is a trifyl in the formula.
Compound 5 in the inventive method ' can be (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R)) or (its structure is following for 5S, 4 ' R) configurations:
Figure G2009100513143D00042
R in the said structure 1, R 2, R 3, Ar and n as previously mentioned.
In the inventive method, the preparation process of above-claimed cpd is with n=1, R 1=R 2=H, (5R, 4 ' S) with (5S, the compound of 4 ' S) configurations are example, can represent with following reaction process simply:
Figure G2009100513143D00043
Can specify as follows the compound method in the above-mentioned reaction process:
Prepare compound 2 from racemic compound 1:
Under rare gas element, in the organic solvent, compound 1 and two trifluoro-methylsulfonyl aniline (PhNTf 2) and alkali reaction, obtain compound 2.Wherein compound 1, two trifluoro-methylsulfonyl aniline (PhNTf 2) and the mol ratio of alkali be 1: 1-2: 1-2, temperature of reaction :-78 ℃-100 ℃, the reaction times: 1-48h.
From compound 2 preparation (5R, 4 ' S) with (5S, the compound 3 of 4 ' S) configurations:
Under rare gas element, in the organic solvent; Compound 2, (S)-amino alcohol and carbon monoxide (CO) are at palladium catalyst, triphenylphosphine, 1; 2-two (diphenylphosphino) ethane (dppe), 1; 3-two (diphenylphosphino) propane (dppp) or 1, the existence of 4-two (diphenylphosphino) butane parts such as (dppb) and lithium salts such as lithium chloride, lithiumbromide or lithium iodide is reaction down, obtains acid amides alcohol.This acid amides alcohol issues sub-intramolecular cyclization reaction estranged in the effect of methane sulfonyl chloride (MsCl) and alkali, again through the separation of diastereomer, obtain respectively (5R, 4 ' S) with (5S, the compound 3 of 4 ' S) configurations.Wherein compound 2 with (S)-mol ratio of amino alcohol is 1: 1-3.The pressure of carbon monoxide is 1-10atm.Palladium catalyst can be Pd (PPh 3) 4, Pd (dba) 2(dba is a dibenzalacetone),, Pd 2(dba) 3, Pd 2(dba) 3CHCl 3, Pd (OAc) 2Deng, the palladium catalyst mole dosage is the 0.1-50% of compound 2, temperature of reaction: 0 ℃-100 ℃, and the reaction times: 1-48h.The mol ratio of acid amides alcohol, methane sulfonyl chloride and alkali is 1: 1-5: 1-30, and temperature of reaction :-78 ℃-100 ℃, the reaction times: 1-48h.
From (5R, 4 ' S) or (5S, compound 3 preparation of 4 ' S) configurations (5S, 4 ' S) or (5R, the compound 4 of 4 ' S) configurations:
Under rare gas element, in the organic solvent, (5R, 4 ' S) or (5S, the compound 3 of 4 ' S) configurations and two trifluoro-methylsulfonyl aniline (PhNTf 2) and alkali reaction, obtain (5S, 4 ' S) or (5R, the compound 4 of 4 ' S) configurations.Wherein the mol ratio of compound 3, two trifluoro-methylsulfonyl anilines and alkali is 1: 1-2: 1-2, and temperature of reaction :-78 ℃-100 ℃, the reaction times: 1-48h.
From (5S, 4 ' S) or (5R, compound 4 preparation of 4 ' S) configurations (5S, 4 ' S) or (5R, the compound 5 of 4 ' S) configurations:
Under rare gas element, in the organic solvent, (5S, 4 ' S) or (5R, the compound 4 and the diaryl phosphine hydrogen Ar of 4 ' S) configurations 2(wherein Ar is phenyl, R to PH xOr/and R x' substituted-phenyl or 2-furyl, described R x, R x' be selected from hydrogen, C respectively 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Perfluoroalkyl, C 5-7Naphthenic base, phenyl, benzyl, (1-phenyl) ethyl, 1-naphthyl, 2-naphthyl or halogen.Recommend Ar for being phenyl, o-methyl-phenyl-or 3,5-3,5-dimethylphenyl etc.) at palladium catalyst and triphenylphosphine (PPh 3), 1,2-two (diphenylphosphino) ethane (dppe), 1 reacts under 3-two (diphenylphosphino) propane (dppp) or 1,4-two (diphenylphosphino) butane parts such as (dppb) exist, and obtains (5S, 4 ' S) or (5R, the compound 5 of 4 ' S) configurations respectively.Wherein compound 4 and Ar 2The mol ratio of PH is 1: 1-5, palladium catalyst can be Pd (PPh 3) 4, Pd (dba) 2(dba is a dibenzalacetone), Pd 2(dba) 3, Pd 2(dba) 3CHCl 3, Pd (OAc) 2Deng, the palladium catalyst mole dosage is the 0.1-50% of compound 4.Temperature of reaction: 0 ℃-150 ℃, the reaction times: 1-48h.
The object of the invention also provides the purposes of part 5 ', and promptly such part can be used for preparing the complex compound 6 ' of iridium.This iridium complex 6 ' can be used as the catalyzer of the asymmetric hydrogenation of polytype group with imine moiety and polytype non-functionalization alkene.This Preparation of catalysts process can be represented with following reaction formula:
Figure G2009100513143D00061
Can specify as follows above-mentioned preparation process:
Under rare gas element, part 5 ', [Ir (cod) Cl] 2(X is hexafluoro-phosphate radical (PF for (cod is 1, the 5-cyclooctadiene) and NaX 6), hexafluoro tellurate radical (SbF 6), tetrafluoroborate (BF 4), tetraphenyl borate (B (Ph) 4), four-(3,5-two trifluoromethyls) borate (BAr F)) in organic solvent, stir and can obtain iridium complex 6 '.Wherein part 5 ', [Ir (cod) Cl] 2With the mol ratio of NaX be 2-100: 1: 1-5, temperature of reaction: 0 ℃-100 ℃, the reaction times: 1-20h.
The iridium complex of above-mentioned preparation can be used for the asymmetric hydrogenation of the polytype group with imine moiety of catalysis and polytype non-functionalization alkene.This catalytic process can specify as follows:
Under rare gas element, in the solution of iridium catalyst, add imines or olefin substrate, charge into H 2, reaction can obtain corresponding asymmetric hydrogenation product at a certain temperature.Wherein the mol ratio of alkene and iridium complex 6 ' is 100-5000: 1, and temperature of reaction: 0 ℃-120 ℃, reaction times: 0.1-100h, H 2Pressure: 0.5-100 normal atmosphere.
The organic solvent that in aforesaid method of the present invention, uses can be benzene,toluene,xylene, trimethylbenzene, acetonitrile, ether, THF, glycol dimethyl ether, chloroform, methylene dichloride, methyl alcohol, ethanol, Virahol, N; Dinethylformamide, DMAC N,N, DMSO 99.8MIN. or N-Methyl pyrrolidone etc.
The alkali that in aforesaid method of the present invention, uses can be sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, cesium carbonate, sodium hydrogencarbonate, saleratus, sodium hydride, potassium hydride KH, hydrolith, triethylamine, diisopropyl ethyl amine, Tetramethyl Ethylene Diamine, N; Accelerine, N; N-Diethyl Aniline, 1; 4-diazabicyclooctane (DABCO), diazabicylo dodecyl (DBU), 1,4-lupetazin, 1-methyl piperidine, 1-methylpyrrole, quinoline, pyridine, n-Butyl Lithium (n-BuLi), lithium diisopropylamine (LDA) and the silica-based Lithamide of two front threes (LiHMDS) etc.
The practical implementation method
Help further to understand the present invention through following embodiment, but do not limit the content of invention.
Preparing method of the present invention and catalytic process can further embody as follows with the preparation process of representative compound and the asymmetric hydrogenation process of representative imines and alkene:
Embodiment 1: from the racemic compound 2 of racemic compound 1 preparation
Under argon atmosphere, in 50mL Schlenk pipe, add hmds 5.4mL (26.2mmol); Anhydrous tetrahydro furan 20mL is cooled to-78 ℃, carefully drips 1.6M n-butyllithium solution 10mL (16mmol);-78 ℃ are stirred 0.5h down, and the tetrahydrofuran solution of processing LiHMDS is subsequent use.
Under argon atmosphere, in a 250mL there-necked flask, add spiral shell diketone 12.0g (13.2mmol), two trifluoro-methylsulfonyl aniline (PhNTf 2) 5.6g (15.7mmol), anhydrous tetrahydro furan 100mL.Reaction system is cooled to-78 ℃.The careful LiHMDS solution for preparing that drips needs 20-30min approximately in reaction solution.Behind the reaction 1h, reaction system slowly rises to room temperature under-78 ℃, and reaction is spent the night.Saturated sodium bicarbonate solution cancellation reaction.Tell organic phase, water is with ethyl acetate extraction three times.The organic phase that merges is used anhydrous sodium sulfate drying.After organic phase removes by filter siccative, boil off solvent.Resistates is through column chromatography (eluent: can get colourless liquid 22.5g petroleum ether/ethyl ether=50/1～20/1).Productive rate 67%.
1H?NMR(300MHz，CDCl 3)δ5.90(t，J＝2.7Hz，1H)，2.52-1.82(m，10H)； 13CNMR(75MHz，CDCl 3)δ217.2，148.3，118.9，118.4(q，J＝314.5Hz)，60.2，36.9，34.0，33.6，26.0，19.5； 19F?NMR(282MHz，CDCl 3)δ-73.84(s).
Embodiment 2: from racemic compound 2 preparation (5R, 4 ' S) with (5S, the compound 3a of 4 ' S) configurations (R wherein 3=Bn)
Under the argon shield, in a hydrogenation bottle, add Pd (dba) 2(182mg, 0.32mmol), triphenylphosphine (182mg, 0.69mmol), Lithium chloride (anhydrous) (818mg, 19mmol), (S)-amphetamine alcohol (1.91g, 12.6mmol), compound 2 (1.8g, 6.3mmol), THF (45mL).Reaction system with the freezing-method of bleeding-the thawing degassing three times after, in glove box, be transferred in the autoclave, charge into carbon monoxide 5atm.Reaction kettle is heated to about 55 ℃ reaction 10h.Behind the cool to room temperature, carefully bleed off excessive carbon monoxide.Reaction solution boils off solvent, and resistates can comprise the acid amides alkylol cpd of a pair of diastereomer through column chromatography purification.Under argon atmosphere, in three-necked bottle, add 4-(N, N-dimethylamino) pyridine (86mg, 0.70mmol), above-mentioned acid amides alkylol cpd, anhydrous methylene chloride (40mL), triethylamine (5.3mL, 25.2mmol).Reaction solution is cooled to-5-0 ℃, and (2.4mL 25.2mmol), continues reaction 1h under this temperature carefully to drip methylsulfonyl chloride.Add triethylamine (24mL), react 24h under the room temperature.Add the methylene dichloride dilute reaction solution, after closing in the saturated sodium bicarbonate solution, dichloromethane extraction three times.The organic phase that merges is used anhydrous sodium sulfate drying.Remove by filter siccative, boil off solvent, resistates carry out column chromatography purification (eluent: petrol ether/ethyl acetate=80/1～20/1), obtain respectively (5R, 4 ' S) with (5S, the compound 3a of 4 ' S) configurations.
(5R, 4 ' S)-3a: productive rate 33% (two steps).White solid.M.p.=105-106 ℃; [α] D 20=+27.4 ° of (c=0.69, CHCl 3); 1H NMR (300MHz, CDCl 3) δ 7.32-7.16 (m, 5H), 6.63 (t, J=2.4Hz, 1H), 4.38-4.31 (m, 1H), 4.18 (t; J=8.4Hz, 1H), 3.91 (t, J=7.2Hz, 1H), 2.91 (dd, J=13.5Hz, 6.9Hz; 1H), and 2.66-2.31 (m, 6H), 2.15-2.05 (m, 2H), 1.92-1.77 (m, 3H); 13CNMR (75MHz, CDCl 3) δ 222.2,159.7,141.3,138.3,134.8,129.3,128.3,126.2,71.2,68.1,61.9,42.0,38.1,36.7,34.6,31.5,20.6; IR (film) v 3061,3026,2958,1737,1659,1601,1496,1474,1386,1155,1056,973,939,920,702cm -1ESI-MS m/z:318.0 [M+Na +], 296.1 [M+H +]; HRMS (MALDI) m/z:calcd.for C 19H 22NO 2: 296.1645, Found:296.1649 [M+H +]; Ultimate analysis (%) theoretical value C 19H 21NO 2: C 77.26, and H 7.17, and N 4.74, experimental value: C 77.59, and H 7.27, N 4.70.
(5S, 4 ' S)-3a: productive rate 35% (two steps).Weak yellow liquid.[α] D 20＝-79.0°(c＝0.45，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.31-7.18(m，5H)，6.60(t，J＝2.1Hz，1H)，4.42-4.34(m，1H)，4.16(t，J＝9.0Hz，1H)，3.93(t，J＝7.2Hz，1H)，2.99(dd，J＝13.5Hz，6.0Hz，1H)，2.65(dd，J＝13.5Hz，7.5Hz，1H)，2.57-2.43(m，4H)，2.27(dd，J＝17.7Hz，7.8Hz，1H)，2.17-2.07(m，2H)，1.95-1.73(m，3H)； 13C?NMR(75MHz，CDCl 3)δ222.4，159.6，141.2，138.2，134.8，129.2，128.3，126.3，71.1，67.7，62.0，41.8，38.0，36.6，34.7，31.5，20.5；IR(film)v?3061，3026，2957，1736，1659，1601，1496，1453，1385，1155，1056，972，920，702cm -1；ESI-MS?m/z：318.0[M+Na +]，296.1[M+H +]；HRMS(ESI)m/z：calcd.for?C 19H 22NO 2：296.1645，Found：296.1649[M+H +].
Embodiment 3: from racemic compound 2 preparation (5R, 4 ' S) with (5S, the compound 3b of 4 ' S) configurations (R wherein 3=Ph)
Adopt the method for embodiment 2, obtain respectively (5R, 4 ' S) with (5S, the compound 3b of 4 ' S) configurations.
(5R, 4 ' S)-3b: productive rate 38% (two steps).White solid.M.p.＝146-147℃；[α] D 20＝+82.8°(c＝0.66，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.36-7.22(m，3H)，7.14(d，J＝6.9Hz，2H)，6.25(br?s，1H)，5.26(t，J＝9.0Hz，1H)，4.59(td，J＝9.4Hz，2.7Hz，1H)，3.95(t，J＝7.8Hz，1H)，2.62-2.45(m，4H)，2.36-2.08(m，3H)，1.99-1.75(m，3H)； 13CNMR(75MHz，CDCl 3)δ222.3，160.9，142.4，142.1，134.4，128.6，127.2，126.3，74.2，69.8，62.1，37.9，36.7，34.6，31.5，20.6.；IR(film)v?2956，2902，1732，1684，1660，1602，1495，1458，1157，972，911，765，723，704cm -1；ESI-MS?m/z：282.1[M+H +]；HRMS(MALDI)m/z：calcd.for?C 18H 20NO 2：282.1489，Found：282.1502[M+H +].
(5S, 4 ' S)-3b: productive rate 39% (two steps).Weak yellow liquid.[α] D 20＝-46.6°(c＝0.58，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.37-7.18(m，5H)，6.77(br?s，1H)，5.23(t，J＝9.6Hz，1H)，4.58(t，J＝9.0Hz，1H)，4.03(t，J＝8.1Hz，1H)，2.64-2.46(m，4H)，2.34-2.07(m，3H)，2.00-1.74(m，3H)； 13C?NMR(75MHz，CDCl 3)δ222.2，160.7，142.7，142.1，134.4，128.5，127.2，126.4，73.9，69.9，62.1，37.9，36.7，34.8，31.4，20.5；IR(film)v3027，2958，1736，1656，1600，1454，1383，1154，1058，960，915，758，700cm -1；ESI-MS?m/z：282.1[M+H +]；HRMS(MALDI)m/z：calcd.for?C 18H 20NO 2：282.1489，Found：282.1499[M+H +].
Embodiment 4: from racemic compound 2 preparation (5R, 4 ' S) with (5S, the compound 3c of 4 ' S) configurations (R wherein 3=iPr)
Adopt the method for embodiment 2, obtain respectively (5R, 4 ' S) with (5S, the compound 3c of 4 ' S) configurations.
(5R, 4 ' S)-3c: productive rate 35% (two steps).Colourless liquid.[α] D 20＝+13.5°(c＝0.57，CHCl 3)； 1HNMR(300MHz，CDCl 3)δ6.58(t，J＝2.4Hz，1H)，4.22-4.16(m，1H)，3.95-3.89(m，2H)，2.61-2.43(m，4H)，2.30(dd，J＝17.7Hz，7.5Hz，1H)，2.18-2.07(m，2H)，1.95-1.63(m，4H)，0.88-0.82(m，6H)； 13C?NMR(75MHz，CDCl 3)δ222.4，159.2，140.7，135.0，72.5，69.5，61.9，38.2，36.7，34.7，32.8，31.5，20.6，18.4，18.3；IR(film)v?2958，2873，1738，1661，1603，1466，1446，1405，1384，1365，1155，1057，970，918，822，718cm -1；ESI-MS?m/z：248.2[M+H +]；HRMS(MALDI)m/z：calcd.forC 15H 22NO 2：248.1645，Found：248.1654[M+H +].
(5S, 4 ' S)-3c: productive rate 36% (two steps).Weak yellow liquid.[α] D 20＝-84.2°(c＝0.57，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.57(t，J＝2.7Hz，1H)，4.21-4.13(m，1H)，3.95-3.87(m，2H)，2.64-2.40(m，4H)，2.29(dd，J＝17.4Hz，7.5Hz，1H)，2.17-2.07(m，2H)，1.94-1.64(m，4H)，0.91(d，J＝6.6Hz，3H)，0.85(d，J＝6.3Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ222.5，159.0，140.6，135.0，72.4，69.5，62.0，38.1，36.7，34.9，32.9，31.5，20.5，18.6，18.5；IR(film)v?2959，2873，1737，1660，1603，1466，1384，1155，1057，970，918cm -1；ESI-MS?m/z：248.2[M+H +]；HRMS(MALDI)m/z：calcd.forC 15H 22NO 2：248.1645，Found：248.1655[M+H +].
Embodiment 5: from racemic compound 2 preparation (5R, 4 ' S) with (5S, the compound 3d of 4 ' S) configurations (R wherein 3=tBu)
Adopt the method for embodiment 2, obtain respectively (5R, 4 ' S) with (5S, the compound 3d of 4 ' S) configurations.
(5R, 4 ' S)-3d: productive rate 37% (two steps).White solid.M.p.＝64-65℃；[α] D 20＝+22.5°(c＝0.85，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.55(t，J＝3.0Hz，1H)，4.14-4.00(m，2H)，3.87-3.81(m，1H)，2.57-2.44(m，4H)，2.34-2.17(m，1H)，2.14-2.07(m，2H)，1.96-1.74(m，3H)，0.82(s，9H)； 13C?NMR(75MHz，CDCl 3)δ222.5，159.0，140.4，135.1，76.1，68.0，61.8，38.3，36.7，34.7，34.0，31.6，25.6，20.7；IR(film)v?2956，2904，2870，1740，1663，1605，1479，1385，1364，1156，1054，972，918，738cm -1；ESI-MSm/z：262.1[M+H +]；HRMS(MALDI)m/z：calcd.for?C 16H 24NO 2：262.1802，Found：262.1805[M+H +].
(5S, 4 ' S)-3d: productive rate 41% (two steps).White solid.M.p.＝54-56℃；[α] D 20＝-110.3°(c＝0.67，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.55(br?s，1H)，4.12(t，J＝9Hz，1H)，4.01(t，J＝6.9Hz，1H)，3.89-3.83(m，1H)，2.63-2.41(m，4H)，2.34-2.25(m，1H)，2.19-2.09(m，2H)，1.96-1.75(m，3H)，0.86(s，9H)； 13C?NMR(75MHz，CDCl 3)δ222.7，158.9，140.4，135.2，75.9，67.9，61.9，38.3，36.7，35.0，34.9，31.5，25.8，20.6；IR(film)v?2957，2905，2870，1739，1662，1605，1478，1383，1364，1155，1053，972，918，738cm -1；ESI-MS?m/z：284.0[M+Na +]，262.1[M+H +]；HRMS(MALDI)m/z：calcd.for?C 16H 24NO 2：262.1802，Found：262.1804[M+H +].
Embodiment 6: from racemic compound 2 preparation (5R, 4 ' S) with (5S, the compound 3e of 4 ' S) configurations (R wherein 3=iBu)
Adopt the method for embodiment 2, obtain respectively (5R, 4 ' S) with (5S, the compound 3e of 4 ' S) configurations.
(5R, 4 ' S)-3e: productive rate 43% (two steps).White solid.M.p.＝44-46℃；[α] D 20＝+19.1°(c＝0.76，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.58(t，J＝2.1Hz，1H)，4.19-4.13(m，1H)，4.07-4.00(m，1H)，3.94-3.89(m，1H)，2.60-2.44(m，4H)，2.33-2.25(m，1H)，2.17-2.07(m，2H)，1.95-1.72(m，3H)，1.55-1.39(m，2H)，1.14-1.05(m，1H)，0.89(t，J＝7.8Hz，3H)，0.76(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ222.3，159.1，140.7，134.9，71.2，69.0，61.9，39.1，38.1，36.7，34.7，31.5，25.6，20.6，14.4，11.5；IR(film)v?2960，2935，1738，1661，1603，1386，1155，1056，972，918cm -1；ESI-MSm/z：262.1[M+H +]；HRMS(ESI)m/z：calcd.for?C 16H 24NO 2：262.1802，Found：262.1796[M+H +].
(5S, 4 ' S)-3e: productive rate 39% (two steps).White solid.M.p.＝70-72℃；[α] D 20＝-118.8°(c＝0.57，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.57(br?s，1H)，4.19-3.88(m，3H)，2.63-2.08(m，7H)，1.94-1.71(m，3H)，1.59-1.43(m，2H)，1.26-1.07(m，1H)，0.91(t，J＝7.5Hz，3H)，0.80(d，J＝6.0Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ222.6，158.9，140.6，135.0，71.0，69.0，62.0，39.2，38.1，36.7，34.8，31.4，25.8，20.6，14.6，11.5；IR(film)v?2960，2931，2876，1739，1661，1603，1457，1379，1154，1056，972，918cm -1；ESI-MS?m/z：262.2[M+H +]；HRMS(ESI)m/z：calcd.for?C 16H 24NO 2：262.1802，Found：262.1805[M+H +].
Embodiment 7: from (5R, the compound 3a of 4 ' S) configurations preparation (5S, the compound 4a of 4 ' S) configurations (R wherein 3=Bn)
Under rare gas element, and the new hmds that steams of adding in Schlenk pipe (0.96mL, 4.2mmol), anhydrous tetrahydro furan (12mL).Be cooled to-78 ℃, (1.6mL, 2.56mmol) ,-78 ℃ are stirred 0.5h down to the n-Butyl Lithium of 1.6M.Under argon atmosphere, in a reaction flask, add N-phenyl two fluoroform sulphonamide (PhNTf 2) (887mg, 2.48mmol), (5R, and 4 ' S)-3a (610mg, 2.07mmol), anhydrous tetrahydro furan (15mL).Be cooled to-78 ℃, carefully add the LiHMDS solution of above-prepared.-78 ℃ of following reaction 1h slowly rise to stirred overnight after the room temperature.After the saturated sodium bicarbonate solution cancellation reaction, water is with ethyl acetate extraction three times.The organic phase that merges is used saturated common salt water washing, anhydrous sodium sulfate drying.Remove by filter siccative, boil off solvent.Resistates is through column chromatography (eluent: petroleum ether/ethyl ether=100/1～30/1) obtain pure (5S, the compound 4a 788mg of 4 ' S) configurations.Productive rate 89%.
Colourless liquid.[α] D 20＝+72.1°(c＝0.76，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.31-7.19(m，5H)，6.62(t，J＝2.4Hz，1H)，5.65(t，J＝2.7Hz，1H)，4.50-4.37(m，1H)，4.16-4.10(m，1H)，3.96-3.91(m，1H)，3.04(dd，J＝13.8Hz，6.3Hz，1H)，2.64-2.18(m，7H)，2.05-1.86(m，2H)； 13C?NMR(75MHz，CDCl 3)δ159.5，151.5，142.0，138.4，133.8，129.3，128.3，126.3，120.6，116.3，114.6，70.6，68.3，58.7，41.7，36.7，34.0，30.6，27.3，26.4； 19F?NMR(282MHz，CDCl 3)δ-74.50(s)；IR(film)v3064，3028，2934，2852，1660，1602，1420，1248，1212，1143，1031，860，701，606cm -1；ESI-MS?m/z：428.2[M+H +]；HRMS(MALDI)m/z：calcd.for?C 20H 21F 3NO 4S：428.1138，Found：428.1140[M+H +].
Embodiment 8: from (5S, the compound 3a of 4 ' S) configurations preparation (5R, the compound 4a of 4 ' S) configurations (R wherein 3=Bn)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～30/1, productive rate 89%.
Colourless liquid.[α] D 20＝-60.5°(c＝0.80，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.31-7.19(m，5H)，6.62(t，J＝2.4Hz，1H)，5.64(t，J＝2.7Hz，1H)，4.50-4.42(m，1H)，4.16-4.11(m，1H)，3.94-3.89(m，1H)，3.07(dd，J＝13.2Hz，5.1Hz，1H)，2.69-2.22(m，7H)，2.05-1.87(m，2H)； 13C?NMR(100MHz，CDCl 3)δ159.5，151.4，142.0，138.2，133.8，129.3，128.4，126.3，120.0，116.8，114.7，70.5，68.0，59.8，41.6，37.2，34.2，30.6，29.7，26.5； 19F?NMR(282MHz，CDCl 3)δ-74.44(s)；IR(film)v?3027，2928，2852，1660，1456，1419，1378，1248，1210，1142，1032，860，700，604cm -1；ESI-MS?m/z：428.0[M+H +]；HRMS(MALDI)m/z：calcd.for?C 20H 21F 3NO 4S：428.1138，Found：428.1132[M+H +].
Embodiment 9: from (5R, the compound 3b of 4 ' S) configurations preparation (5S, the compound 4b of 4 ' S) configurations (R wherein 3=Ph)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 90%.
Colourless liquid.[α] D 20＝+70.4°(c＝0.53，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.35-7.18(m，5H)，6.72(t，J＝2.7Hz，1H)，5.65(t，J＝2.9Hz，1H)，5.29(t，J＝9.3Hz，1H)，4.60-4.54(m，1H)，3.98(t，J＝8.1Hz，1H)，2.67-2.22(m，6H)，2.10-1.92(m，2H)； 13C?NMR(100MHz，CDCl 3)δ160.6，151.4，142.6，142.5，133.6，128.5，127.3，126.4，118.5(q，J＝318.3Hz)，114.9，73.6，70.1，59.9，36.5，34.1，30.6，26.5； 19FNMR(282MHz，CDCl 3)δ-74.37(s)；IR(film)v?3030，2937，2853，1660，1602，1420，1249，1212，1142，1033，859，699，609cm -1；ESI-MS?m/z：436.0[M+Na +]，414.0[M+H +]；HRMS(MALDI)m/z：calcd.for?C 19H 29F 3NO 4S：414.0981，Found：414.1001[M+H +].
Embodiment 10: from (5S, the compound 3b of 4 ' S) configurations preparation (5R, the compound 4b of 4 ' S) configurations (R wherein 3=Ph)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 92%.
Colourless liquid.[α] D 20＝-71.7°(c＝0.58，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.36-7.20(m，5H)，6.73(t，J＝2.7Hz，1H)，5.65-5.64(m，1H)，5.27(t，J＝9.0Hz，1H)，4.61-4.55(m，1H)，4.00(t，J＝8.1Hz，1H)，2.69-2.26(m，6H)，2.09-1.92(m，2H)； 13C?NMR(75MHz，CDCl 3)δ160.5，151.3，142.8，142.6，133.7，128.6，127.3，126.4，114.9，73.6，59.8，37.2，34.4，30.7，26.5； 19F?NMR(282MHz，CDCl 3)δ-74.40(s)；IR(film)v?3064，3030，2938，2853，1660，1602，1420，1142，1032，951，860，699，605cm -1；ESI-MS?m/z：414.0[M+H +]；HRMS(ESI)m/z：calcd.for?C 19H 29F 3NO 4S：414.0981，Found：414.0980[M+H +].
Embodiment 11: from (5R, the compound 3c of 4 ' S) configurations preparation (5S, the compound 4c of 4 ' S) configurations (R wherein 3=iPr)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=200/1～100/1), productive rate 93%.
Colourless liquid.[α] D 20＝51.4°(c＝0.49，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.58(t，J＝3.0Hz，1H)，5.62(t，J＝2.1Hz，1H)，4.21-4.13(m，1H)，3.98-3.90(m，2H)，2.70-2.61(m，1H)，2.50-2.31(m，4H)，2.27-2.18(m，1H)，2.04-1.87(m，2H)，1.75-1.64(m，1H)，0.92(d，J＝6.6Hz，3H)，0.85(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ158.8，151.4，141.2，134.0，118.4(q，J＝318Hz)，114.4，72.9，69.0，59.8，36.7，34.2，32.9，30.6，26.5，18.6，18.2； 19F?NMR(282MHz，CDCl 3)δ-74.46(s)；IR(film)v?2960，1663，1604，1421，1379，1249，1214，1144，1033，1006，955，860，607cm -1；ESI-MS?m/z：380.0[M+H +]；HRMS(ESI)m/z：calcd.forC 16H 21F 3NO 4S：380.1138，Found：380.1141[M+H +].
Embodiment 12: from (5S, the compound 3c of 4 ' S) configurations preparation (5R, the compound 4c of 4 ' S) configurations (R wherein 3=iPr)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1, productive rate 95%.
Colourless liquid.[α] D 20＝-120.5°(c＝0.44，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.59(t，J＝2.7Hz，1H)，5.64(t，J＝2.7Hz，1H)，4.21-4.15(m，1H)，3.99-3.87(m，2H)，2.71-2.61(m，1H)，2.55-2.23(m，5H)，2.03-1.86(m，2H)，1.79-1.68(m，1H)，0.93(d，J＝6.6Hz，3H)，0.87(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ158.7，151.4，141.3，134.0，118.4(q，J＝318Hz)，114.5，72.6，68.9，59.7，37.3，34.3，32.8，30.6，26.6，18.7，18.3； 19F?NMR(282MHz，CDCl 3)δ-74.44(s)；IR(film)v2928，2859，1718，1654，1597，1495，1422，1376，1209，1141，950，751，694，604cm -1；ESI-MS?m/z：380.0[M+H +]；HRMS(MALDI)m/z：calcd.for?C 16H 21F 3NO 4S：380.1138，Found：380.1153[M+H +].
Embodiment 13: from (5R, the compound 3d of 4 ' S) configurations preparation (5S, the compound 4d of 4 ' S) configurations (R wherein 3=tBu)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～50/1), productive rate 92%.
Colourless liquid.[α] D 20＝-86.6°(c＝0.59，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.56(t，J＝2.4Hz，1H)，5.62(t，J＝2.7Hz，1H)，4.14-3.87(m，3H)，2.69-2.65(m，1H)，2.53-2.20(m，5H)，2.03-1.89(m，2H)，0.88(s，9H)； 13C?NMR(75MHz，CDCl 3)δ158.6，151.3，141.1，134.0，114.6，76.4，67.3，59.8，36.8，34.3，34.0，30.6，26.6，25.6； 19F?NMR(282MHz，CDCl 3)δ-74.45(s)；IR(film)v?2955，2869，1664，1604，1421，1249，1211，1143，1032，1008，955，859，606cm -1；ESI-MS?m/z：394.2[M+H +]；HRMS(ESI)m/z：calcd.for?C 17H 22F 3NO 4S：394.1294，Found：394.1288[M+H +].
Embodiment 14: from (5S, the compound 3d of 4 ' S) configurations preparation (5R, the compound 4d of 4 ' S) configurations (R wherein 3=tBu)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～70/1, productive rate 98%.
Colourless liquid.[α] D 20＝56.7°(c＝0.44，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.57(s，1H)，5.63(t，J＝2.4Hz，1H)，4.15-4.09(m，1H)，4.02-3.87(m，2H)，2.72-2.63(m，1H)，2.53-2.24(m，5H)，2.02-1.87(m，2H)，0.87(s，9H)； 13C?NMR(100MHz，CDCl 3)δ158.6，151.4，141.0，134.1，120.0，116.9，114.4，76.3，67.4，59.8，37.5，34.5，33.9，30.6，26.6，25.9； 19F?NMR(282MHz，CDCl 3)δ-74.42(s)；IR(film)v?2958，2907，2870，1664，1605，1420，1364，1249，1220，1142，1033，956，915，859，605；ESI-MSm/z：416.0[M+Na +]，394.0[M+H +]；HRMS(MALDI)m/z：calcd.for?C 17H 22F 3NO 4S：394.1294，Found：394.1293[M+H +].
Embodiment 15: from (5R, the compound 3e of 4 ' S) configurations preparation (5S, the compound 4e of 4 ' S) configurations (R wherein 3=iBu)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～80/1), productive rate 87%.
Colourless liquid.[α] D 20＝+50.8°(c＝0.91，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.58(s，1H)，5.61(t，J＝2.4Hz，1H)，4.18-4.02(m，2H)，3.92(t，J＝7.2Hz，1H)，2.68-2.59(m，1H)，2.50-2.31(m，4H)，2.27-2.17(m，1H)，2.04-1.87(m，2H)，1.54-1.45(m，2H)，1.19-1.06(m，1H)，0.90(t，J＝7.2Hz，3H)，0.79(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ158.6，151.4，141.2，133.9，118.3(q，J＝318.9Hz)，142.3(d，J＝1.4Hz)，71.4，68.4，59.7，39.1，36.6，34.1，30.5，26.5，25.8，14.2，11.3； 19F?NMR(282MHz，CDCl 3)δ-74.46(s)；IR(film)v?2963，2935，2878，1662，1604，1421，1375，1249，1211，1144，1033，956，914，859，604cm -1；ESI-MS?m/z：394.2[M+H +]；HRMS(MALDI)m/z：calcd.for?C 17H 22F 3NO 4S：394.1294，Found：394.1291[M+H +].
Embodiment 16: from (5S, the compound 3e of 4 ' S) configurations preparation (5R, the compound 4e of 4 ' S) configurations (R wherein 3=iBu)
Adopt the method among the embodiment 7, eluent: petrol ether/ethyl acetate=100/1～70/1, productive rate 99%.
Colourless viscous liquid.[α] D 20＝+107.2°(c＝0.50，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ6.59(br?s，1H)，5，63(d，J＝2.1Hz，1H)，4.19-4.07(m，2H)，3.90(t，J＝7.2Hz，1H)，2.65-2.22(m，6H)，2.03-1.86(m，2H)，1.64-1.47(m，2H)，1.21-1.11(m，1H)，0.91(t，J＝7.5Hz，3H)，0.81(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ158.6，151.4，141.2，134.0，118.4(q，J＝318Hz)，114.4，71.4，68.4，59.7，39.1，37.2，34.3，30.5，26.5，25.9，14.4，11.4； 19F?NMR(282MHz，CDCl 3)δ-74.4(s)；IR(film)v?2963，2935，1662，1604，1421，1376，1249，1217，1143，1032，956，915，860，606；ESI-MSm/z：394.2[M+H +]；HRMS(MALDI)m/z：calcd.for?C 17H 22F 3NO 4S：394.1294，Found：394.1293[M+H +].
Embodiment 17: from (5S, the compound 4a of 4 ' S) configurations preparation (5S, 4 ' ' S) the compound 5a of configuration (R wherein 3=Bn, Ar=Ph)
Under argon shield, (3.4mg, 0.015mmol), (7.6mg 0.018mmol) adds in a Schlenk pipe dppb, adds toluene 1mL with palladium.After stirring 0.5h under the room temperature, add (5S, and 4 ' S)-4a (61mg, 0.143mmol), toluene 1mL, diisopropyl ethyl amine (74 μ L, 0.53mmol).Reaction system with the freezing-method of bleeding-the thawing degassing three times after, add HPAr 2(39 μ L, 0.2mmol), 80 ℃ of reaction 24h.Boil off solvent, resistates directly carries out column chromatography (eluent: petrol ether/ethyl acetate=50/1～20/1), get (5S, the 5a 30mg of 4 ' S) configurations.Productive rate 45%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.51-7.47(m，1H)，7.36-7.19(m，14H)，6.59(dt，J＝18.0Hz，3.0Hz，1H)，5.75-5.65(m，1H)，4.42-4.39(m，1H)，4.09(dt，J＝26.4Hz，8.7Hz，1H)，3.96-3.82(m，1H)，3.10(ddd，J＝33.3Hz，13.2Hz，5.1Hz，1H)，2.64-2.23(m，6H)，2.05-1.84(m，3H)； 31P?NMR(121MHz，CDCl 3)δ-26.13(s).
Embodiment 18: from (5R, the compound 4a of 4 ' S) configurations preparation (5R, the compound 5a of 4 ' S) configurations (R wherein 3=Bn, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=50/1～30/1, productive rate 68%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.39-7.19(m，15H)，6.46(br?s，1H)，5.69(br?s，1H)，4.28-4.23(m，1H)，3.88(t，J＝8.7Hz，1H)，3.75(t，J＝7.5Hz，1H)，3.03(dd，J＝14.4Hz，5.7Hz，1H)，2.66-2.39(m，6H)，2.13-2.08(m，1H)，1.97-1.88(m，2H)； 31P?NMR(121MHz，CDCl 3)δ-25.68(s).
Embodiment 19: from (5S, the compound 4b of 4 ' S) configurations preparation (5S, the compound 5b of 4 ' S) configurations (R wherein 3=Ph, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 40%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.57-7.51(m，2H)，7.38-7.23(m，9H)，7.14-7.00(m，4H)，6.65(t，J＝3.0Hz，1H)，5.69-5.66(m，1H)，5.25(t，J＝9.3Hz，1H)，4.56-4.50(m，1H)，3.99(t，J＝8.4Hz，1H)，2.70-2.32(m，5H)，1.97-1.81(m，3H)； 31P?NMR(121MHz，CDCl 3)δ-26.08(s).
Embodiment 20: from (5R, the compound 4b of 4 ' S) configurations preparation (5R, the compound 5b of 4 ' S) configurations (R wherein 3=Ph, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 38%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ＝7.43-7.17(m，15H)，6.57(br?s，1H)，5.69(t，J＝3.0Hz，1H)，5.08(t，J＝9.0Hz，1H)，4.34-4.28(m，1H)，3.83(t，J＝8.1Hz，1H)，2.73-2.37(m，5H)，2.18-2.14(m，1H)，2.02-1.91(m，2H)ppm； 31P?NMR(121MHz，CDCl 3)δ＝-25.16(s)ppm.
Embodiment 21: from (5S, the compound 4c of 4 ' S) configurations preparation (5S, the compound 5c of 4 ' S) configurations (R wherein 3=iPr, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 53%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.53-7.48(m，2H)，7.36-7.34(m，3H)，7.25-7.22(m，5H)，6.52(s，1H)，5.68-5.66(m，1H)，4.14-4.08(m，1H)，3.92-3.82(m，2H)，2.77-2.67(m，1H)，2.53-2.30(m，4H)，2.02-1.72(m，4H)，0.98(d，J＝6.6Hz，3H)，0.87(d，J＝7.2Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-25.98(s)；ESI-MS?m/z：432.2[M+O+H +]，416.2[M+H +]；HRMS(MALDI)m/z：calcd.for?C 27H 31NOP：416.2138，Found：416.2133[M+H +].
Embodiment 22: from (5R, the compound 4c of 4 ' S) configurations preparation (5R, the compound 5c of 4 ' S) configurations (R wherein 3=iPr, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 56%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.43-7.42(m，10H)，6.41(br?s，1H)，6.68-6.66(m，1H)，4.00-3.95(m，1H)，3.86-3.74(m，2H)，2.62-2.37(m，5H)，2.20-2.06(m，1H)，1.93-1.86(m，2H)，1.84-1.68(m，1H)，0.94(d，J＝6.9Hz，3H)，0.86(d，J＝6.6Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-25.63(s).
Embodiment 23: from (5R, the compound 4d of 4 ' S) configurations preparation (5R, the compound 5d of 4 ' S) configurations (R wherein 3=tBu, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～70/1, productive rate 56%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.46-7.22(m，10H)，6.38(br?s，1H)，5.67(t，J＝3.0Hz，1H)，3.96-3.83(m，3H)，2.68-2.64(m，1H)，2.55-2.37(m，4H)，2.10-2.07(m，1H)，1.91-1.83(m，2H)，0.88(s，9H)； 31P?NMR(121MHz，CDCl 3)δ-25.65(s).
Embodiment 24: from (5S, the compound 4e of 4 ' S) configurations preparation (5S, the compound 5e of 4 ' S) configurations (R wherein 3=iBu, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 37%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.54-7.47(m，2H)，7.37-7.34(m，3H)，7.26-7.22(m，5H)，6.52(s，1H)，5.68-5.66(m，1H)，4.13-3.97(m，2H)，3.86(t，J＝7.5Hz，1H)，2.74-2.65(m，1H)，2.52-2.34(m，4H)，1.99-1.74(m，3H)，1.65-1.48(m，2H)，1.28-1.13(m，1H)，0.91(t，J＝7.2Hz，3H)，0.82(d，J＝6.9Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-25.94(s)；ESI-MS?m/z：446[M+O+H +]，430.2[M+H +]；HRMS(MALDI)m/z：calcd.for?C 28H 33NOP：430.2294，Found：430.2293[M+H +].
Embodiment 25: from (5R, the compound 4e of 4 ' S) configurations preparation (5R, the compound 5e of 4 ' S) configurations (R wherein 3=iBu, Ar=Ph)
Adopt the method among the embodiment 17, eluent: petrol ether/ethyl acetate=100/1～70/1, productive rate 37%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.42-7.24(m，10H)，6.42(br?s，1H)，5.68-5.66(m，1H)，3.95-3.91(m，2H)，3.80-3.72(m，1H)，2.71-2.28(m，5H)，2.18-2.07(m，1H)，1.94-1.85(m，2H)，1.54-1.47(m，2H)，1.23-1.11(m，1H)，0.91(t，J＝7.5Hz，3H)，0.79(d，J＝6.6Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-25.66(s)；ESI-MS?m/z：446.2[M+O+H +]，430.2[M+H +]；HRMS(MALDI)m/z：calcd.forC 28H 33NOP：430.2294，Found：430.2292[M+H +].
Embodiment 26: from (5R, the compound 4a of 4 ' S) configurations preparation (5R, the compound 5f of 4 ' S) configurations (R wherein 3=Bn, Ar=o-Tol)
Adopt the method among the embodiment 17, with (o-Tol) 2PH replaces Ph 2PH, eluent: petrol ether/ethyl acetate=100/1～50/1, productive rate 53%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.32-7.03(m，13H)，6.47(s，1H)，5.45(t，J＝2.7Hz，1H)，4.34-4.29(m，1H)，3.90-3.75(m，2H)，3.04(dd，J＝13.5Hz，8.1Hz，1H)，2.83-2.72(m，2H)，2.62-2.50(m，2H)，2.44-2.25(m，9H)，1.95-1.85(m，2H)； 31P?NMR(121MHz，CDCl 3)δ-44.31(s).
Embodiment 27: from (5R, the compound 4c of 4 ' S) configurations preparation (5R, the compound 5g of 4 ' S) configurations (R wherein 3=iPr, Ar=o-Tol)
Adopt the method among the embodiment 17, with (o-Tol) 2PH replaces Ph 2PH, eluent: petrol ether/ethyl acetate=100/1, productive rate 85%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.23-7.00(m，8H)，6.43(s，1H)，5.44-5.42(m，1H)，4.00-3.94(m，1H)，3.87-3.75(m，2H)，2.82-2.74(m，2H)，2.52-2.23(m，10H)，1.91-1.82(m，2H)，1.72-1.65(m，1H)，0.94(d，J＝6.6Hz，3H)，0.86(d，J＝6.9Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-43.90(s).
Embodiment 28: from (5R, the compound 4d of 4 ' S) configurations preparation (5R, the compound 5h of 4 ' S) configurations (R wherein 3=tBu, Ar=o-Tol)
Adopt the method among the embodiment 17, with (o-Tol) 2PH replaces Ph 2PH, eluent: petrol ether/ethyl acetate=150/1～100/1, productive rate 42%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.26-7.10(m，6H)，7.07-6.98(m，2H)，6.40(s，1H)，5.44-5.42(m，1H)，3.95-3.79(m，3H)，2.89-2.11(m，1H)，2.74-2.66(m，1H)，2.54-2.21(m，10H)，1.92-1.82(m，2H)，0.87(s，9H)； 31P?NMR(121MHz，CDCl 3)δ-43.75(s)；ESI-MS?m/z：474.2[M+O+H +]，458.2[M+H +]；HRMS(MALDI)m/z：calcd.for(C 30H 37NOP+O)：474.2556，Found：474.2567[M+O+H +].
Embodiment 29: from (5R, the compound 4e of 4 ' S) configurations preparation (5R, the compound 5i of 4 ' S) configurations (R wherein 3=iBu, Ar=o-Tol)
Adopt the method among the embodiment 17, with (o-Tol) 2PH replaces Ph 2PH, eluent: petrol ether/ethyl acetate=100/1, productive rate 68%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.26-7.00(m，8H)，6.43(br?s，1H)，5.43(d，J＝2.7Hz，1H)，3.96-3.91(m，2H)，3.81-3.74(m，1H)，2.82-2.69(m，2H)，2.56-2.23(m，10H)，1.91-1.81(m，2H)，1.56-1.49(m，2H)，1.18-1.11(m，1H)，0.91(t，J＝6.6Hz，3H)，0.80(d，J＝6.6Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-43.95(s)；ESI-MS?m/z：474.2[M+O+H +]，458.2[M+H +]；HRMS(MALDI)m/z：calcd.forC 30H 37NOP：458.2607，Found：458.2603[M+H +].
Embodiment 30: from (5R, the compound 4c of 4 ' S) configurations preparation (5R, the compound 5j of 4 ' S) configurations (R wherein 3=iPr, Ar=Xyl)
Adopt the method among the embodiment 17, with (Xyl) 2PH replaces Ph 2PH, eluent: petrol ether/ethyl acetate=100/1～70/1, productive rate 25%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.04(d，J＝8.4Hz，2H)，6.94-6.86(m，4H)，6.41(s，1H)，5.67-5.66(m，1H)，4.05(t，J＝7.8Hz，1H)，3.94-3.86(m，1H)，3.80(t，J＝7.8Hz，1H)，2.72-2.63(m，1H)，2.55-2.24(m，16H)，2.15-2.06(m，1H)，1.93-1.80(m，2H)，1.73-1.64(m，1H)，0.94(d，J＝6.6Hz，3H)，0.87(d，J＝6.6Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-25.61(s)..
Embodiment 31: from (5R, the compound 4c of 4 ' S) configurations preparation (5R, the compound 5j of 4 ' S) configurations (R wherein 3=iBu, Ar=Xyl)
Adopt the method among the embodiment 17, with (Xyl) 2PH replaces Ph 2PH, eluent: petrol ether/ethyl acetate=150/1～70/1, productive rate 21%.
Colourless viscous liquid. 1H?NMR(300MHz，CDCl 3)δ7.03(d，J＝6.3Hz，2H)，6.95-6.93(m，2H)，6.86(s，1H)，6.42(s，1H)，5.68(t，J＝2.1Hz，1H)，4.03-3.97(m，2H)，3.82-3.78(m，1H)，2.70-2.63(m，1H)，2.54-2.36(m，3H)，2.33-2.30(m，1H)，2.28(s，6H)，2.24(s，6H)，2.13-2.06(m，1H)，1.92-1.82(m，2H)，1.55-1.47(m，2H)，1.18-1.48(m，1H)，0.92(t，J＝2.7Hz，3H)，0.80(d，J＝4.8Hz，3H)； 31P?NMR(121MHz，CDCl 3)δ-26.76(s).
Embodiment 32: from (5S, the compound 5a of 4 ' S) configurations preparation (5S, the compound 6a of 4 ' S) configurations (R wherein 3=Bn, Ar=Ph)
Under argon shield, in Schlenk pipe, add [Ir (cod) Cl] 2(23mg, 0.034mmol), (5S, and 4 ' S)-5a (30mg, 0.065mmol), degassing methylene dichloride (5mL).Back flow reaction 2h.Be cooled to room temperature, add NaBAr F(79mg, 0.089mmol), vigorous stirring 1h under the room temperature.Add the water (3mL) of the degassing, stir 1h under the room temperature.Tell dichloromethane layer, water is with dichloromethane extraction three times.Boil off solvent, resistates is through column chromatography (eluent: sherwood oil/methylene dichloride=1/1) can get pure iridium complex 62mg, productive rate 57%.
Red bubble powder solid, M.p.=49-51 ℃; [α] D 20=+66.7 ° of (c0.33, CHCl 3); 1H NMR (300MHz, CDCl 3) δ 7.94-7.89 (m, 2H), 7.71 (s, 8H), 7.65-7.62 (m, 2H), 7.51 (s, 4H), 7.40-7.35 (m, 3H); 7.28-7.12 (m, 6H), 6.89-6.86 (m, 2H), 6.51-6.40 (m, 2H), 4.80-4.76 (m, 2H), 4.04 (t, J=9.6Hz; 1H), 3.87 (t, J=9.3Hz, 1H), 3.55 (br s, 1H), 3.36 (dd, J=12.9Hz, 4.4Hz, 1H); 3.14 (br s, 1H), 3.08-2.92 (m, 1H), 2.77-2.59 (m, 4H), 2.52-2.25 (m, 6H), 2.17-1.92 (m, 7H); 31P NMR (161MHz, CDCl 3) δ 4.39 (s); 19F NMR (282MHz, CDCl 3) δ-62.79 (s); IR (film) v 2926,2854,1609,1354,1278,1126,804,682cm -1MS (MALDI) m/z:764.3 [M-BAr F] +HRMS (MALDI) m/zcalcd.for C 39H 42NOP 191Ir +([M-BAr F] +): 762.2604, Found:762.2595.
Embodiment 33: from (5R, the compound 5a of 4 ' S) configurations preparation (5R, the compound 6a of 4 ' S) configurations (R wherein 3=Bn, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=1/1, productive rate 89%.
Red powder.M.p.＝103-105℃；[α] D 20＝-4°(c0.30，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.76-7.70(m，10H)，7.56-7.41(m，12H)，7.30-7.23(m，3H)，6.92-6.90(m，2H)，6.37-6.34(m，2H)，4.80-4.76(m，1H)，4.59-4.56(m，1H)，4.45-4.40(m，2H)，4.08-4.00(m，1H)，3.50-3.48(m，1H)，3.36-3.33(m，1H)，3.20-3.16(m，1H)，2.61-2.47(m，3H)，2.32-1.94(m，10H)，1.86-1.78(m，1H)，1.68-1.52(m，3H)； 13CNMR(100MHz，CDCl 3)δ169.3，161.7(q，J＝49.8Hz)，151.8，140.3，138.0，137.6，134.8，134.5，134.3，133.7，133.6，133.3，133.2，131.7(d，J＝2.2Hz)，131.6(d，J＝2.2Hz)，129.8，129.3(m)，129.1，129.0(m)，128.7(m)，128.6，128.4(m)，128.1，127.8，127.7，127.1，125.9，123.2，120.5，117.5(m)，90.6(d，J＝11.2Hz)，85.6(d，J＝13.4Hz)，74.4，68.0，67.8，66.9，65.9，61.6，40.7，37.6，37.5(d，J＝6.7Hz)，34.5(d，J＝4.4Hz)，32.4，32.2，32.0，31.8，30.0(d，J＝3.0Hz)，29.7，27.4(d，J＝2.2Hz)； 31P?NMR(161MHz，CDCl 3)δ1.05(s)； 19F?NMR(282MHz，CDCl 3)δ-62.41(s)；IR(film)v2927，1663，1609，1436，1396，1354，1277，1124，886，839，713，682，670cm -1；MS(MALDI)m/z：764.3[M-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 39H 42NOP 191Ir +([M-BAr F] +)：762.2604，Found：762.2593.
Embodiment 34: from (5S, the compound 5b of 4 ' S) configurations preparation (5S, the compound 6b of 4 ' S) configurations (R wherein 3=Ph, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=1/1, productive rate 73%.
Orange powder.M.p.＝197-198℃；[α] D 20＝99.3°(c＝0.33，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.99-7.92(m，2H)，7.72-7.67(m，11H)，7.52(s，4H)，7.41-7.32(m，6H)，7.19-7.13(m，2H)，7.02-6.99(m，2H)，6.52-6.47(m，2H)，4.04-4.21(m，3H)，3.28-3.06(m，4H)，2.76-2.65(m，4H)，2.49-2.33(m，3H)，2.13-1.78(m，6H)，1.62-1.50(m，1H)，1.44-1.26(m，2H)； 13C?NMR(75MHz，CDCl 3)δ168.1(d，J＝1.1Hz)，161.7(q，J＝49.8Hz)，155.2，139.3，139.1，138.6，137.6，135.3，134.8，134.2，134.1，132.1(d，J＝2.4Hz)，131.5，131.4，131.1(d，J＝2.6Hz)，130.6，130.2，129.9，129.7，129.5(m)，129.4，129.3，129.1(m)，128.9，128.7，128.6(m)，128.4，128.2(m)，127.5，126.8，126.3，122.7，119.1，117.5(m)，91.1(d，J＝13.1Hz)，89.8(d，J＝13.0Hz)，78.2，69.1，67.7，67.5，62.2，59.1，39.1，34.5(d，J＝6.0Hz)，33.6(d，J＝3.5Hz)，33.5，33.4，31.9，30.8(d，J＝2.6Hz)，30.3(m)，30.2，29.9，29.7，28.2； 31P?NMR(121MHz，CDCl 3)δ3.19(s)； 19F?NMR(282MHz，CDCl 3)δ-62.80(s)；IR(film)v?2961，1673，1601，1395，1354，1276，1246，1126，1096，886，839，715，682，669；MS(MALDI)m/z：750.3[M-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 38H 40NOP 191Ir：748.2448，Found：748.2446[M-BAr F] +.
Embodiment 35: from (5R, the compound 5b of 4 ' S) configurations preparation (5R, the compound 6b of 4 ' S) configurations (R wherein 3=Ph, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=1/1, productive rate 69%.
Red powder.M.p.＝172-174℃；[α] D 20＝-11°(c＝0.29，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.87-7.81(m，2H)，7.72(s，8H)，7.58-7.19(m，15H)，6.92-6.86(m，2H)，6.28(s，1H)，6.10(d，J＝7.8Hz，1H)，5.49-5.43(m，1H)，5.21-5.19(m，1H)，4.90(t，J＝9.9Hz，1H)，4.61-4.55(m，1H)，4.38-4.22(m，1H)，3.00-2.89(m，2H)，2.57-2.22(m，5H)，2.08-1.69(m，6H)，1.55-1.43(m，2H)，1.34-1.26(m，2H)，1.20-1.06(m，1H)； 13C?NMR(75MHz，CDCl 3)δ170.0(d，J＝1.0Hz)，161.7(q，J＝49.0Hz)，146.6(d，J＝3.7Hz)，140.6，138.6，138.5，138.0，135.7，135.5，134.8，132.9，132.7，132.6，132.2(d，J＝2.5Hz)，130.9(d，J＝2.3Hz)，130.0，129.6，129.5(m)，129.1(m)，128.8，128.7(m)，128.2(m)，128.1，127.3，126.9，126.5，126.3，122.7，119.1，117.5(m)，90.8(d，J＝9.4Hz)，81.4(d，J＝15.6Hz)，76.3，71.2，70.1，69.1，68.9，60.0，40.7(d，J＝6.3Hz)，35.8，35.0(m)，34.4，33.7，32.6，31.6，31.5，30.1，29.7，28.5(d，J＝1.8Hz)，25.8(d，J＝3.0Hz)； 31P?NMR(121MHz，CDCl 3)δ3.12(s)； 19FNMR(282MHz，CDCl 3)δ-62.80(s)；IR(film)v?2960，1676，1600，1458，1437，1352，1276，1166，1129，887，715，682，669cm -1；MS(MALDI)m/z：750.3[M-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 38H 40NOP 191Ir：748.2448，Found：748.2436[M-BAr F] +.
Embodiment 36: from (5S, the compound 5c of 4 ' S) configurations preparation (5S, the compound 6c of 4 ' S) configurations (R wherein 3=iPr, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 87%.
Orange red powder.M.p.＝201-203℃；[α] D 20＝+80.7°(c＝0.60，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.88-7.81(m，2H)，7.71(s，8H)，7.58-7.52(m，7H)，7.41-7.34(m，3H)，7.18-7.12(m，2H)，6.51-6.46(m，1H)，6.41(s，1H)，4.69-4.65(m，2H)，4.12(t，J＝8.1Hz，1H)，3.76(t，J＝9.6Hz，1H)，3.38-3.36(m，1H)，3.14-3.12(m，1H)，2.76-2.65(m，4H)，2.44-2.28(m，5H)，2.09-1.87(m，8H)，1.51-1.41(m，1H)，0.70-0.67(m，6H)； 13C?NMR(75MHz，CDCl 3)δ168.5(d，J＝1.2Hz)，161.7(q，J＝49.8Hz)，155.1，138.9，138.6，138.3，135.7，134.8，134.3，134.1，132.0(d，J＝3.1Hz)，131.7，131.6，131.1(d，J＝2.4Hz)，130.6，129.9(d，J＝6.1Hz)，129.5(m)，129.3，129.2，129.1(m)，128.8，128.6(m)，128.2(m)，127.6，126.9，126.3，122.7，119.1，117.4(m)，91.7(d，，J＝4.0Hz)，88.1(d，J＝13.4Hz)，70.9(d，J＝2.5Hz)，67.6，67.4，62.4，58.8，39.1，34.6(m)，34.4(d，J＝6.1Hz)，33.5(d，J＝10.9Hz)，31.9，31.5，29.7，29.3，27.8(d，J＝1.8Hz)，19.4，14.3； 31P?NMR(121MHz，CDCl 3)δ3.78(s)； 19FNMR(282MHz，CDCl 3)δ-62.80(s)；IR(film)v?2930，1670，1602，1436，1389，1352，1276，1168，1129，900，886，838，716，682，669cm -1；MS(MALDI)m/z：716.3[M-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 35H 42NOP 191Ir：714.2604，Found：714.2582[M-BAr F] +.
Embodiment 37: from (5R, the compound 5c of 4 ' S) configurations preparation (5R, the compound 6c of 4 ' S) configurations (R wherein 3=iPr, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 93%.
Orange red powder.M.p.＝172-173℃；[α] D 20＝-9.2°(c＝0.37，CHCl 3)； 1HNMR(300MHz，CDCl 3)δ7.84-7.77(m，2H)，7.72(s，8H)，7.53-7.36(m，12H)，6.27(s，1H)，6.21(d，J＝7.5Hz，1H)，5.04(s，1H)，4.49(t，J＝12.3Hz，1H)，4.35-4.29(m，3H)，3.28-3.15(m，1H)，3.12-2.50(m，1H)，2.50-2.26(m，4H)，2.15-1.74(m，10H)，1.53-1.14(m，3H)，0.99(d，J＝6.9Hz，3H)，0.83(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ169.3(d，J＝1.1Hz)，161.7(q，J＝48.9Hz)，147.4(d，J＝2.8Hz)，142.5，140.7，138.4，137.8，135.3，135.1，134.7，133.3，133.1，133.0，132.1(d，J＝2.3Hz)，131.4(d，J＝2.0Hz)，129.9，129.5，129.4(m)，129.0(m)，128.8，128.7(m)，128.2(m)，127.3，126.5，126.3，122.7，119.1，117.4(m)，91.5(d，J＝9.5Hz)，83.9(d，J＝16.2Hz)，71.1，69.8，69.2，68.5，68.3，60.6，40.2(d，J＝6.7Hz)，40.1，35.8，35.3(d，J＝5.6Hz)，33.1，32.4，31.7，31.5，31.5，31.4，31.2，29.7，28.6，26.0(d，J＝2.3Hz)，19.0，15.7； 31P?NMR(121MHz，CDCl 3)δ2.64(s)； 19F?NMR(282MHz，CDCl 3)δ-62.79(s)；IR(film)v?2961，1699，1653，1558，1507，1437，1352，1275，1167，1130，886，778，715，682，669cm -1；MS(MALDI)m/z：716.3[M-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 35H 42NOP 191Ir：714.2604，Found：714.2587[M-BAr F] +.
Embodiment 38: from (5R, the compound 5d of 4 ' S) configurations preparation (5R, the compound 6d of 4 ' S) configurations (R wherein 3=tBu, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 79%.
Orange powder.M.p.＝192-194℃；[α] D 20＝+44.2°(c＝0.31，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ8.08-8.01(m，2H)，7.71(s，8H)，7.59-7.47(m，9H)，7.36-7.26(m，3H)，6.27-6.25(m，2H)，6.30-6.28(m，1H)，4.52-4.38(m，2H)，4.33-4.27(m，1H)，4.00-3.95(m，1H)，3.10-2.90(m，2H)，2.60-2.39(m，3H)，2.26-1.62(m，10H)，1.53-1.32(m，3H)，1.28(s，9H)； 13C?NMR(75MHz，CDCl 3)δ169.4(d，J＝1.9Hz)，161.7(q，J＝48.8Hz)，144.3(d，J＝3.8Hz)，141.9，139.3，138.8，136.4，136.2，134.8，133.9，132.5，132.4(d，J＝2.2Hz)，131.9，131.7，131.2(d，J＝2.1Hz)，129.9，129.5(m)，129.3，129.1(m)，128.7(m)，128.5，128.1(m)，127.8，127.7，127.5(m)，127.0，126.3，126.3，122.7，119.1，117.5(m)，91.1(d，J＝6.9Hz)，79.7(d，J＝18.9Hz)，76.3，72.5，70.1，68.9，68.8，59.5，41.1(d，J＝6.5Hz)，35.9(d，J＝5.4Hz)，35.1，33.8(2peaks)，32.8，31.0(d，J＝12.2Hz)，29.7，27.8(d，J＝2.6Hz)，26.1，25.1(d，J＝2.8Hz)； 31P?NMR(121MHz，CDCl 3)δ3.30(s)； 19F?NMR(282MHz，CDCl 3)δ-62.78(s)；IR(film)v?2961，1590，1352，1276，1666，1130，886，801，715，682，669cm -1；MS(MALDI)m/z：730.3[M-BAr F] +；HRMS(MALDI)m/z?calcd.forC 36H 44NOP 191Ir：728.2761，Found：728.2740[M-BAr F] +.
Embodiment 39: from (5S, the compound 5e of 4 ' S) configurations preparation (5S, the compound 6e of 4 ' S) configurations (R wherein 3=iBu, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1.5/1, productive rate 83%.
Orange red solid.M.p.＝128-130℃；[α] D 20＝+89.3°(c＝0.63，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.88-7.73(m，10H)，7.53(s，7H)，7.41-7.35(m，3H)，7.25-7.13(m，2H)，6.48(d，J＝7.8Hz，1H)，6.41(s，1H)，4.71-4.65(m，2H)，4.09(t，J＝9.0Hz，1H)，3.77-3.70(m，1H)，3.38(br?s，1H)，3.16(br?s，1H)，2.76-2.27(m，8H)，2.14-1.88(m，6H)，1.68-1.43(m，3H)，1.05-0.95(m，2H)，0.88-0.80(m，1H)，0.73(t，J＝7.5Hz，3H)，0.66(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ168.5(d，J＝1.0Hz)，161.7(q，J＝50.2Hz)，155.1，139.0，138.6，138.4，135.8，134.8，134.2，134.0，132.0(d，J＝2.5Hz)，131.6，131.5，131.1(d，J＝2.4Hz)，130.5，130.0，129.8，129.5(m)，129.4，129.2，129.1(m)，128.8，128.7(m)，128.3(m)，127.6，126.9，126.3，122.7，119.1，117.4(m)，91.6(d，J＝12.1Hz)，87.9(d，J＝13.4Hz)，71.0，69.4，67.6，67.4，62.3，58.8，39.1，36.3，34.6(m)，34.5，34.4，33.6，33.4，31.9，31.4，29.8，27.9，26.8，12.3，11.5； 31P?NMR(121MHz，CDCl 3)δ3.74(s)； 19F?NMR(282MHz，CDCl 3)δ-62.83(s)；IR(film)v?2968，1670，1601，1436，1352，1276，1167，1130，886，838，715，682，669cm -1；MS(MALDI)m/z：730.9([M-BAr F] +)，622.9([M-COD-BAr F])；HRMS(MALDI)m/z?calcd.for?C 36H 44NOP 191Ir：728.2761，Found：728.2745[M-BAr F] +.
Embodiment 40: from (5R, the compound 5e of 4 ' S) configurations preparation (5R, the compound 6e of 4 ' S) configurations (R wherein 3=iBu, Ar=Ph)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 95%.
Orange red solid.M.p.＝158-161℃；[α] D 20＝-7.5°(c＝0.43，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.84-7.78(m，2H)，7.71(s，8H)，7.56-7.48(m，12H)，6.25(s，1H)，6.21(d，J＝8.1Hz，1H)，5.07(s，1H)，4.45-4.31(m，4H)，3.26(s，1H)，3.10-3.01(m，1H)，2.50-2.24(m，4H)，2.13-1.75(m，11H)，1.53-1.16(m，4H)，0.95(t，J＝7.5Hz，3H)，0.76(d，J＝6.6Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ169.4，161.7(q，J＝49.4Hz)，147.4(m)，140.7，138.4，138.0，135.4，135.3，134.8，133.4，133.3，133.2，132.1(d，J＝2.2Hz)，131.5(d，J＝2.2Hz)，129.5(d，J＝1.1Hz)，129.3(m)，129.1(m)，128.7(m)，128.6，128.4(m)，127.3，126.8，125.9，123.2，120.5，117.5(m)，91.5(d，J＝9.3Hz)，83.8(d，J＝15.3Hz)，69.6，69.3(m)，68.6，68.4，60.6，40.3(d，J＝6.7Hz)，38.6，36.0，35.3(d，J＝4.8Hz)，33.1，32.4，31.5，31.4，29.7，28.7，26.4，26.2，12.7，11.5； 31P?NMR(121MHz，CDCl 3)δ2.83(s)； 19F?NMR(282MHz，CDCl 3)δ-62.79(s)；IR(film)v?2923，1677，1599，1437，1352，1275，1167，1129，897，887，838，801，715，682，669cm -1；MS(MALDI)m/z：728.3[M-BAr F] +；HRMS(MALDI)m/zcalcd.for?C 36H 44NOP 191Ir：728.2761，Found：728.2753[M-BAr F] +
Embodiment 41: from (5R, the compound 5f of 4 ' S) configurations preparation (5R, the compound 6f of 4 ' S) configurations (R wherein 3=Bn, Ar=o-Tol)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 82%.
Orange red spumescence solid.M.p.＝152-153℃；[α] D 20＝13.1°(c＝0.31，CHCl 3)； 1HNMR(300MHz，CDCl 3)δ9.27(q，J＝7.5Hz，1H)，7.71(s，8H)，7.60-7.55(m，1H)，7.51(s，4H)，7.47-7.28(m，7H)，7.24-7.05(m，4H)，6.09-6.06(m，2H)，5.36-5.33(m，1H)，4.74-4.70(m，1H)，4.47(t，J＝9.9Hz，1H)，4.38-4.28(m，2H)，4.07-4.02(m，1H)，2.87-2.83(m，1H)，2.71-2.50(m，8H)，2.20(s，3H)，2.17-1.69(m，10H)，1.45-0.76(m，3H)； 13C?NMR(75MHz，CDCl 3)δ172.1，161.7(q，J＝49.7Hz)，146.3(m)，145.3，142.3，142.2，141.8，140.3，140.1，134.8，134.4，134.3，133.3(d，J＝6.7Hz)，133.0(d，J＝2.4Hz)，132.2(m)，131.8，130.6，129.9，129.5，129.1(m)，128.7(m)，128.3，128.2(m)，128.1，126.3，126.2，125.9(m)，125.6，125.0，123.7，123.0，122.7，119.1，117.4(m)，89.5(d，J＝8.6Hz)，77.9(d，J＝15.8Hz)，74.6，73.2，69.2，69.0，67.3，59.7，44.4，42.6(d，J＝7.3Hz)，36.1，34.3，33.7，31.9，31.5，31.3，29.7，25.9，25.0，24.8，22.8(d，J＝3.7Hz)； 31P?NMR(121MHz，CDCl 3)δ2.55(s)； 19FNMR(282MHz，CDCl 3)δ-62.78(s)；IR(film)v?2927，1670，1590，1456，1354，1277，1125，887，839，713，682，670cm -1；MS(MALDI)m/z：790.3[M-BAr F] +，682.2[M-COD-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 41H 46NOP 191Ir：790.2917，Found：790.2921[M-BAr F] +.
Embodiment 42: from (5R, the compound 5g of 4 ' S) configurations preparation (5R, the compound 6g of 4 ' S) configurations (R wherein 3=iPr, Ar=o-Tol)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1.5/1, productive rate 81%.
Orange/yellow solid.M.p.=200-201 ℃; [α] D 20=-16.8 ° of (c=0.31, CHCl 3); 1H NMR (300MHz, CDCl 3) δ 9.22 (q, J=7.8Hz, 1H), 7.73 (s, 8H), 7.56-7.53 (m, 5H), 7.43-7.32 (m, 4H); 7.18-7.14 (m, 1H), 7.08-7.02 (m, 1H), 6.08-6.02 (m, 2H), 5.22 (brs, 1H), 4.39-4.21 (m; 3H), 4.19-4.16 (m, 1H), 2.86-2.83 (m, 1H), 2.70 (s, 3H), 2.57-2.47 (m, 5H); 2.38 (s, 3H), 2.19-1.68 (m, 9H), 1.39-1.20 (m, 4H), 0.96-0.74 (m, 6H); 13C NMR (75MHz, CDCl 3) δ 171.4,161.7 (q, J=49.7Hz), 145.4,145.3,143.2,142.5,142.1,140.4 (d, J=11.5Hz), 135.1,134.8; 134.6,133.2,133.1,132.8 (d, J=2.5Hz), 132.5 (d, J=6.1Hz), 132.2,132.1,131.7 (d, J=1.8Hz), 130.3; 129.9,129.5 (m), 129.1 (m), 128.6 (m), 128.2 (m), 126.3,126.1,125.9,125.8,125.7,125.6,125.1; 123.6,122.9,122.7,119.1,117.4 (m), 89.7 (d, J=7.9Hz), 80.5 (d, J=16.4Hz), 77.4,73.3,69.9; 69.0,68.9,67.9,59.7,42.5 (d, J=6.7Hz), 35.7 (d, J=5.5Hz), 34.1,33.6,31.7; 31.3,31.1,27.9 (d, J=1.8Hz), 25.7,24.7,24.5,23.1 (d, J=3.0Hz), 18.9,13.8; 31P NMR (121MHz, CDCl 3) δ 2.57 (s); 19F NMR (282MHz, CDCl 3) δ-74.45 (s); IR (film) v 2961,1683,1592,1457,1385,1352,1275,1167,1128,887,838,716,681,669cm -1MS (MALDI) m/z:744.3 [M-BAr F] +HRMS (MALDI) m/z calcd.forC 37H 46NOP 191Ir:742.2917, Found:742.2918 [M-BAr F] +. ultimate analysis (%) experimental value C 69H 58BF 24IrNOP+C 6H 14: C 53.20, and H 4.29, and N 0.83. measured value: C 52.94, and H 4.15, N 0.94.
Embodiment 43: from (5R, the compound 5h of 4 ' S) configurations preparation (5R, the compound 6h of 4 ' S) configurations (R wherein 3=tBu, Ar=o-Tol)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1.5/1, productive rate 83%.
Orange red solid.M.p.＝179-181℃；[α] D 20＝+37.5°(c＝0.60，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ9.35(q，J＝7.2Hz，1H)，7.72(s，8H)，7.58-7.52(m，4H)，7.45-7.32(m，4H)，7.17-7.11(m，1H)，7.05-6.99(m，1H)，6.14(t，J＝2.7Hz，1H)，6.04(d，J＝8.1Hz，1H)，5.28(br?s，1H)，4.49-4.31(m，3H)，4.18-4.08(m，2H)，2.67(br?s，1H)，2.61(s，3H)，2.59-1.61(m，18H)，1.23-1.20(m，1H)，1.18(s，9H)； 13CNMR(75MHz，CDCl 3)δ171.0(d，J＝0.9Hz)，161.7(q，J＝49.1Hz)，145.4，144.6(m)，142.4，142.1，140.1，139.9，135.8，135.3，134.8，133.1(d，J＝6.7Hz)，132.7(m)，132.3，132.2，132.1，131.6(d，J＝2.4Hz)，130.9，129.9，129.5(m)，129.1(m)，128.8，128.7(m)，128.2(m)，126.3，125.9，125.7，125.6，124.8，124.3，124.2，123.6，122.7，119.1，117.4(m)，89.7(d，J＝7.3Hz)，79.6(d，J＝17.6Hz)，74.5，72.1，71.8，69.5，69.1，68.9，58.0，42.5(d，J＝6.7Hz)，35.8(d，J＝5.5Hz)，34.3(d，J＝3.0Hz)，34.1，31.6，31.1，31.0，30.3，29.7，27.9，27.8(d，J＝2.5Hz)，27.7，26.1，25.5，25.4，25.2(d，J＝3.0Hz)，23.0，22.9，19.1； 31P?NMR(121MHz，CDCl 3)δ1.62(s)； 19F?NMR(282MHz，CDCl 3)δ-62.79(s)；IR(film)v?2961，1653，1591，1558，1512，1457，1353，1276，1166，1128，885，796，735，715，682，668cm -1；MS(MALDI)m/z：758.3[M-BAr F] +，650.2[M-COD-BAr F]；HRMS(MALDI)m/z?calcd.for?C 38H 48NOP 191Ir：756.3074，Found：756.3074[M-BAr F] +.
Embodiment 44: from (5R, the compound 5i of 4 ' S) configurations preparation (5R, the compound 6i of 4 ' S) configurations (R wherein 3=iBu, Ar=o-Tol)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 83%.
Orange red solid.Productive rate 83%.M.p.＝180-183℃；[α] D 20＝-16.1°(c＝0.51，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ9.25(q，J＝7.2Hz，1H)，7.72(br?s，8H)，7.58-7.52(m，5H)，7.45-7.34(m，4H)，7.19-7.15(m，1H)，7.09-7.02(m，1H)，6.07-6.00(m，2H)，5.27(br?s，1H)，4.54-4.49(m，1H)，4.38-4.35(m，2H)，4.24-4.19(m，1H)，2.82-2.79(m，1H)，2.69(s，3H)，2.57-2.29(m，5H)，2.13(s，3H)，2.09-1.69(m，9H)，1.42-1.20(m，6H)，0.98(t，J＝7.2Hz，3H)，0.82(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ117.6(d，J＝1.8Hz)，161.7(q，J＝49.7Hz)，144.4(d，J＝3.7Hz)，145.3，143.1，142.4，142.1，140.5，140.4，135.2，134.8，134.6，133.1(d，J＝6.7Hz)，132.9(d，J＝2.5Hz)，132.6(d，J＝6.1Hz)，132.1(d，J＝7.9Hz)，131.7(d，J＝2.5Hz)，130.4，130.0，129.5(m)，129.1(m)，128.7(m)，128.3(m)，126.3，126.1，125.9，125.7(2peak)，125.6，123.7，123.0，122.7，119.1，117.6-117.3(m)，89.7(d，J＝7.9Hz)，80.0(d，J＝16.4Hz)，73.4，69.1，68.9，68.5，68.0，59.6，42.5(d，J＝6.0Hz)，38.6，35.8(d，J＝4.9Hz)，34.2，33.8，31.7，31.2(d，J＝12.1Hz)，27.9，26.4，25.6，24.6，24.5，23.0(d，J＝3.7Hz)，12.0，11.6； 31P?NMR(121MHz，CDCl 3)δ2.52(s)； 19F?NMR(282MHz，CDCl 3)δ-62.80(s)；IR(Film)v?2972，2840，1671，1592，1507，1458，1387，1352，1275，1167，1128，1030，900，886，834，776，716，681，668cm -1；MS(MALDI)m/z：648.5[M-COD-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 38H 48NOP 191Ir：756.3074，Found：756.3073[M-BAr F] +.
Embodiment 45: from (5R, the compound 5j of 4 ' S) configurations preparation (5R, the compound 6j of 4 ' S) configurations (R wherein 3=iBu, Ar=o-Tol)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 99%.
Orange red solid.M.p.＝95-98℃；[α] D 20＝-6°(c＝0.26，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.71(br?s，8H)，7.52(br?s，4H)，7.46(d，J＝11.7Hz，2H)，7.18(s，1H)，7.10-7.06(m，3H)，6.25(s，1H)，6.17(br?d，J＝8.4Hz，1H)，5.03(t，J＝9.0Hz，1H)，4.44-4.30(m，3H)，4.21-4.16(m，1H)，3.27(br?s，1H)，3.09-3.05(m，1H)，2.52-1.69(m，25H)，1.50-1.33(m，3H)，1.19-1.07(m，1H)，1.01(d，J＝6.6Hz，3H)，0.80(d，J＝3.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ169.3(d，J＝1.1Hz)，161.7(q，J＝49.9Hz)，146.5(d，J＝3.1Hz)，140.4，138.8(d，J＝4.9Hz)，138.8，138.7(d，J＝4.7Hz)，138.2，134.8，133.7(d，J＝2.4Hz)，133.5，133.2，133.1，130.7，130.6，130.0，129.5(m)，129.1(m)，128.7(m)，128.4，128.3(m)，126.7，126.3，126.1，122.8，119.1，117.5(m)，90.4(d，J＝9.2Hz)，82.0(d，J＝16.3Hz)，71.2，69.9(d，J＝8.3Hz)，68.6，68.4，60.8，40.6(d，J＝6.4Hz)，35.6(d，J＝4.9Hz)，35.5，33.5，32.5，31.9，31.4，31.3，29.7，28.6(d，J＝2.7Hz)，26.0(d，J＝3.1Hz)，21.4，21.3，18.8，16.1； 31P?NMR(121MHz，CDCl 3)δ2.71(s)； 19F?NMR(282MHz，CDCl 3)δ-62.82(s)；IR(Film)v?2962，1684，1653，1608，1576，1507，1457，1354，1277，1163，1126，1018，797，742，713，682，670cm -1；MS(MALDI)m/z：772.3[M-BAr F] +，662.2[M-COD-BAr F] +；HRMS(MALDI)m/z?calcd.for?C 39H 50NOP 191Ir：770.3230，Found：770.3208[M-BAr F] +.
Embodiment 46: from (5R, the compound 5k of 4 ' S) configurations preparation (5R, the compound 6k of 4 ' S) configurations (R wherein 3=iBu, Ar=o-Tol)
Adopt the method among the embodiment 32, eluent: sherwood oil/methylene dichloride=2/1～1/1, productive rate 80%.
Orange red solid.M.p.＝124-125℃；[α] D 20＝-10°(c＝0.26，CHCl 3)； 1H?NMR(300MHz，CDCl 3)δ7.71(s，8H)，7.52(s，4H)，7.43(d，J＝11.7Hz，2H)，7.18-7.09(m，4H)，6.24(s，1H)，6.16(d，J＝7.8Hz，1H)，5.03(br?s，1H)，4.47-4.22(m，4H)，3.31(br?s，1H)，3.10-3.05(m，1H)，2.48-2.27(m，15H)，2.13-1.70(m，10H)，1.53-1.16(m，6H)，0.97(t，J＝8.2Hz，3H)，0.80(d，J＝8.2Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ169.3，161.7(q，J＝50.2Hz)，146.7(d，J＝2.6Hz)，140.2，138.9，138.8，138.7，138.6(2peak)，138.1，134.8，133.6(m)，133.1，133.0，130.9，130.8，130.0，129.5(m)，129.2(m)，128.7(m)，128.5，128.3(m)，126.9，126.3，126.2，122.7，119.1，117.6(m)，90.3(d，J＝8.7Hz)，82.1(d，J＝16.0Hz)，69.7(d，J＝2.2Hz)，69.3，68.7，68.5，60.8，40.5(d，J＝6.6Hz)，38.7，35.8，35.6(d，J＝5.0Hz)，33.3，32.5，31.5，31.3，29.7，28.7，26.3，26.1，21.4，21.2，12.8，11.6； 31P?NMR(121MHz，CDCl 3)δ2.63(s)； 19F?NMR(282MHz，CDCl 3)δ-62.83(s)；IR(film)v?2963，1684，1653，1608，1558，1541，1507，1457，1354，1277，1163，1126，887，796，714，682，670cm -1；MS(MALDI)m/z：784.3[M-BAr F] +，676.2[M-COD-BAr F] +；HRMS(MALDI)m/z?calcd.forC 40H 52NOP 191Ir：784.3387，Found：784.3366[M-BAr F] +.
The asymmetric hydrogenation (I) of embodiment 47:N-(1-styrene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-styrene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:91%.Primary product is (R).
1H?NMR(300MHz，CDCl 3)δ7.39-7.20(m，5H)，7.09(t，J＝7.8Hz，2H)，6.64(t，J＝7.2Hz，1H)，6.51(d，J＝8.1Hz，2H)； 13C?NMR(75MHz，CDCl 3)δ147.2，145.2，129.1，128.6，126.8，125.8，117.2，113.2，53.4，25.0；EI-MS(70V)m/z：197(M +，21.9)，196(74.6)，182(23.4)，120(32.8)，105(62.2)，93(18.6)，91(100.0)，77(35.8).
The asymmetric hydrogenation (II) of embodiment 48:N-(1-styrene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol); Add 290mg substrate N-(1-styrene) aniline (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, 10 ℃ are reacted 20h down.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:92%.Primary product is (R).
1H?NMR(300MHz，CDCl 3)δ7.39-7.20(m，5H)，7.09(t，J＝7.8Hz，2H)，6.64(t，J＝7.2Hz，1H)，6.51(d，J＝8.1Hz，2H)； 13C?NMR(75MHz，CDCl 3)δ147.2，145.2，129.1，128.6，126.8，125.8，117.2，113.2，53.4，25.0；EI-MS(70V)m/z：197(M +，21.9)，196(74.6)，182(23.4)，120(32.8)，105(62.2)，93(18.6)，91(100.0)，77(35.8).
The asymmetric hydrogenation of embodiment 49:N-(1-(4-p-methoxy-phenyl) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(4-p-methoxy-phenyl) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:83%.
1H?NMR(300MHz，CDCl 3)δ7.31-7.25(m，2H)，7.12-7.06(m，2H)，6.88-6.83(m，2H)，6.66-6.61(m，1H)，6.53-6.50(m，2H)，4.44(q，J＝6.9Hz，1H)，3.99(br?s，1H)，3.78(s，3H)，1.49(d，J＝6.3Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ158.4，147.3，137.2，129.1，126.8，117.1，113.9，113.2，55.2，52.8，25.0；EI-MS(70V)m/z：227(M +，16.6)，212(8.2)，136(10.6)，135(100.0)，134(7.8)，105(14.4)，91(7.2)，77(9.5).
The asymmetric hydrogenation of embodiment 50:N-(1-(4-aminomethyl phenyl) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(4-aminomethyl phenyl) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:88%.
1H?NMR(300MHz，CDCl 3)δ7.27-7.24(m，2H)，7.14-7.06(m，4H)，6.64(t，J＝8.4Hz，1H)，6.51(dd，J＝8.7Hz，1.2Hz，2H)，4.46(q，J＝6.6Hz，1H)，4.01(br?s，1H)，2.32(s，3H)，1.50(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.3，142.2，136.3，129.2，129.0，125.7，117.1，113.2，53.1，25.0，21.0；EI-MS(70V)m/z：211(M +，39.8)，196(64.2)，119(100.0)，117(14.4)，104(17.9)，93(35.7)，91(24.9)，77(20.9).
The asymmetric hydrogenation of embodiment 51:N-(1-(4-chloro-phenyl-) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(4-chloro-phenyl-) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:92%.
1H?NMR(300MHz，CDCl 3)δ7.32-7.26(m，4H)，7.12-7.06(m，2H)，6.66(t，J＝7.5Hz，1H)，6.47(dd，J＝8.7Hz，0.9Hz，2H)，4.45(q，J＝6.9Hz，1H)，4.01(br?s，1H)，1.49(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ146.9，143.8，132.3，129.1，128.8，127.2，117.4，113.2，52.9，25.1；EI-MS(70V)m/z：233(M ++2，25.4)，231(M +，72.9)，218(35.1)，216(100.0)，141(30.6)，139(89.8)，103(50.7)，93(56.1)，77(39.1).
The asymmetric hydrogenation of embodiment 52:N-(1-(4-bromophenyl) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(4-bromophenyl) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency: 99%, ee:91%.
1H?NMR(300MHz，CDCl 3)δ7.43(dd，J＝8.7Hz，1.8Hz，2H)，7.25(d，J＝7.8Hz，2H)，7.12-7.06(m，2H)，6.66(t，J＝7.2Hz，1H)，6.47(d，J＝7.5Hz，2H)，4.43(q，J＝6.6Hz，1H)，4.01(br?s，1H)，1.49(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ146.9，144.3，131.7，129.1，127.6，120.4，117.5，113.2，53.0，25.1；EI-MS(70V)m/z：277(M ++2，46.2)，276(M ++1，47.8)，275(M +，6.8)，274(49.7)，261(91.8)，260(82.0)，259(89.4)，183(48.4)，104(100.0)，93(81.9).
The asymmetric hydrogenation of embodiment 53:N-(1-(3-chloro-phenyl-) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(3-chloro-phenyl-) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:93%.
1H?NMR(300MHz，CDCl 3)δ7.36(s，1H)，7.26-7.18(m，3H)，6.66(t，J＝7.5Hz，1H)，6.50-6.47(m，2H)，4.44(q，J＝6.6Hz，1H)，4.01(br?s，1H)，1.50(d，J＝7.2Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.6，146.9，134.5，129.9，129.1，127.0，126.0，124.0，117.5，113.2，53.2，25.0；EI-MS(70V)m/z：232(M+，41.1)，218(36.8)，217(32.7)，215(100.0)，139(23.8)，103(30.7)，93(43.3)，77(31.7).
The asymmetric hydrogenation of embodiment 54:N-(1-(3-bromophenyl) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(3-bromophenyl) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:93%.
1H?NMR(300MHz，CDCl 3)δ7.51(s，1H)，7.35-7.27(m，2H)，7.20-7.07(m，3H)，6.66(t，J＝7.5Hz，1H)，6.48-6.45(m，2H)，4.40(q，J＝7.2Hz，1H)，3.99(br?s，1H)，1.47(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.8，146.8，130.2，130.0，129.1，128.9，124.4，122.7，117.5，113.2，53.1，25.1；EI-MS(70V)m/z：277(M ++2，21.9)，275(M +，23.3)，262(53.9)，260(57.7)，120(32.5)，104(84.4)，103(32.5)，93(100.0)，77(71.5)，51(25.2).
The asymmetric hydrogenation of embodiment 55:N-(1-(4-trifluoromethyl) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(4-trifluoromethyl) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:92%.
1H?NMR(300MHz，CDCl 3)δ7.57(d，J＝8.1Hz，2H)，7.47(d，J＝7.8Hz，2H)，7.09(t，J＝7.2Hz，2H)，6.69-6.64(m，1H)，6.48-6.45(m，2H)，4.52(q，J＝6.6Hz，1H)，4.02(br?s，1H)，1.51(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ149.5，146.8，129.3，129.2，126.1，125.6(q，J＝3.8Hz)，117.6，113.2，53.2，25.0； 19F?NMR(282MHz，CDCl 3)δ-62.69(s)；EI-MS(70V)m/z：265(M +，35.6)，251(16.3)，250(100.0)，173(15.8)，133(19.5)，120(15.5)，93(61.8)，77(34.7).
The asymmetric hydrogenation of embodiment 56:N-(1-(2-naphthyl) ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-(2-naphthyl) ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:95%.
1H?NMR(300MHz，CDCl 3)δ7.82-7.78(m，4H)，7.52-7.40(m，3H)，7.10-7.05(m，2H)，6.63(t，J＝7.5Hz，1H)，6.56-6.53(m，2H)，4.63(q，J＝6.6Hz，1H)，4.12(brs，1H)，1.58(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.3，142.7，133.5，132.7，129.1，128.5，127.8，127.6，126.0，125.5，124.4，124.2，117.3，113.3，53.7，25.0；EI-MS(70V)m/z：247(M +，24.3)，232(22.6)，155(100.0)，154(33.2)，153(26.5)，152(14.4)，93(18.0)，77(19.8).
The asymmetric hydrogenation of embodiment 57:4-methoxyl group-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 4-methoxyl group-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:90%.
1H?NMR(300MHz，CDCl 3)δ7.37-7.19(m，5H)，6.68(d，J＝8.4Hz，2H)，6.48(d，J＝8.7Hz，2H)，4.40(q，J＝6.6Hz，1H)，3.68(s，3H)，1.49(d，J＝6.9Hz，3H). 13C?NMR(75MHz，CDCl 3)δ152.0，145.1，141.1，128.6，126.8，125.9，114.8，114.7，55.7，54.5，24.9；EI-MS(70V)m/z：227(M +，73.4)，212(78.6)，123(59.5)，122(20.0)，108(54.8)，105(100.0)，79(20.1)，77(33.8).
The asymmetric hydrogenation of embodiment 58:4-methyl-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 4-methyl-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency: 97%, ee:92%.
1H?NMR(300MHz，CDCl 3)δ7.38-7.19(m，5H)，6.90(d，J＝8.1Hz，2H)，6.43(dd，J＝8.4Hz，2.7Hz，2H)，4.45(q，J＝6.8Hz，1H)，3.91(br?s，1H)，2.18(s，3H)，1.50(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ145.4，145.0，129.5，128.6，126.8，126.3，125.8，113.3，53.6，25.1，20.3；EI-MS(70V)m/z：211(52.4，M +)，197(17.3)，196(100.0)，107(42.6)，106(26.9)，105(45.9)，79(14.4)，77(17.5).
The asymmetric hydrogenation of embodiment 59:3-methyl-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 3-methyl-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:87%.
1H?NMR(300MHz，CDCl 3)δ7.38-7.29(m，4H)，7.24-7.19(m，1H)，6.97(t，J＝8.1Hz，1H)，6.31(s，1H)，6.30(d，J＝8.1Hz，1H)，4.47(q，J＝6.6Hz，1H)，3.97(br?s，1H)，2.21(s，3H)，1.50(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.3，145.3，138.8，129.0，128.6，126.8，125.8，118.1，114.1，110.2，53.3，25.0，21.6；EI-MS(70V)m/z：211(M +，49.1)，197(15.7)，196(100.0)，107(50.7)，106(21.2)，105(63.5)，91(20.5)，77(21.1).
The asymmetric hydrogenation of embodiment 60:2-methyl-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 2-methyl-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency: 97%, ee:73%.
1H?NMR(300MHz，CDCl 3)δ7.38-7.20(m，5H)，7.05(d，J＝7.2Hz，1H)，6.95(t，J＝7.8Hz，1H)，6.60(t，J＝7.2Hz，1H)，6.35(d，J＝8.1Hz，1H)，4.53(q，J＝6.6Hz，1H)，3.86(br?s，1H)，2.22(s，3H)，1.56(dd，J＝6.6Hz，0.9Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ145.2，145.1，129.9，128.6，127.0，126.8，125.7，121.5，116.8，111.0，53.3，25.2，17.6；EI-MS(70V)m/z：211(M +，63.8)，196(90.8)，194(81.9)，107(57.8)，106(36.2)，105(100.0)，91(49.1)，77(46.4).
The asymmetric hydrogenation of embodiment 61:4-chloro-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 4-chloro-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:88%.
1H?NMR(300MHz，CDCl 3)δ7.34-7.21(m，5H)，7.05-7.00(m，2H)，6.44-6.39(m，2H)，4.43(q，J＝6.9Hz，1H)，4.06(br?s，1H)，1.51(d，J＝7.2Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ145.7，144.6，128.9，128.7，127.0，125.7，121.7，114.3，53.5，25.0；EI-MS(70V)m/z：233(M ++2，13.0)，231(M +，38.4)，218(20.9)，216(63.9)，129(14.5)，127(44.5)，105(100.0)，79(15.3)，77(17.4).
The asymmetric hydrogenation of embodiment 62:4-bromo-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 4-bromo-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:89%.
1H?NMR(300MHz，CDCl 3)δ7.32-7.15(m，5H)，7.13-7.11(m，2H)，6.39-6.35(m，2H)，4.42(q，J＝6.3Hz，1H)，4.07(br?s，1H)，1.50(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ146.1，144.5，131.7，128.7，127.0，125.7，114.8，108.7，53.4，24.9；EI-MS(70V)m/z：277(M ++2，12.4)，275(M +，12.6)，262(16.9)，260(17.4)，173(16.3)，171(15.4)，105(100.0)，79(12.9)，77(21.1).
The asymmetric hydrogenation of embodiment 63:2-chloro-N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 2-chloro-N-(1-phenyl ethylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency: 82%, ee:64%.
1H?NMR(300MHz，CDCl 3)δ7.35-7.20(m，6H)，6.97-6.92(m，1H)，6.58-6.53(m，1H)，6.39(d，J＝8.1Hz，1H)，4.69(br?s，1H)，4.55-4.47(m，1H)，1.57(d，J＝6.6Hz，1H)； 13C?NMR(75MHz，CDCl 3)δ144.5，143.0，128.9，128.7，127.6，127.0，125.7，118.9，117.1，112.5，53.3，25.1；EI-MS(70V)m/z：231(M ++2，9.4)，229(M +，29.7)，218(15.5)，216(49.8)，129(14.4)，127(45.2)，105(100.0)，103(15.1)，77(27.2)
Embodiment 64:3, the asymmetric hydrogenation of 5-dimethyl--N-(1-phenyl ethylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate 3 again, 5-dimethyl--N-(1-phenyl ethylidene) aniline (0.15mmol); Connect hydrogen balloon,, be cooled to 10 ℃ with the interior air of hydrogen exchange reaction flask three times.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency: 88%, ee:79%.
1H?NMR(300MHz，CDCl 3)δ7.37-7.17(m，5H)，6.31(s，1H)，6.15(s，2H)，4.46(q，J＝6.9Hz，1H)，3.89(br?s，1H)，2.15(s，6H)，1.47(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.3，145.4，138.7，128.5，126.7，125.8，119.2，111.1，53.2，24.9，21.4；EI-MS(70V)m/z：225(M +，44.6)，211(18.2)，210(100.0)，121(59.7)，105(74.0)，103(18.7)，79(21.8)，77(38.4).
The asymmetric hydrogenation of embodiment 65:4-chloro-N-(1-(4-p-methoxy-phenyl) ethylidene) aniline
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R, 4 ' S)-6c (0.0015mmol); Add substrate 4-chloro-N-(1-(4-p-methoxy-phenyl) ethylidene) aniline (0.15mmol) again; Connect hydrogen balloon,, be cooled to 10 ℃ with the interior air of hydrogen exchange reaction flask three times.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:91%.
1H?NMR(300MHz，CDCl 3)δ7.32-7.29(m，4H)，6.75-6.66(m，2H)，6.46-6.41(m，2H)，4.38(q，J＝6.6Hz，1H)，3.77(br?s，1H)，3.70(s，3H)，1.47(d，J＝6.3Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ151.9，144.0，141.1，132.3，128.7，127.2，114.7，114.5，55.6，53.7，25.2；EI-MS(70V)m/z：263(M ++2，19.3)，261(M +，62.2)，246(48.9)，139(85.8)，123(100.0)，122(46.2)，108(65.8)，103(55.9)，77(36.6).
The asymmetric hydrogenation of embodiment 66:N-(1-phenyl propylidene) aniline
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6c (0.0015mmol) adds substrate N-(1-phenyl propylidene) aniline (0.15mmol) again, connects hydrogen balloon; With the air in the hydrogen exchange reaction flask three times, be cooled to 10 ℃.Add the anhydrous ethylene dichloride of 1.5mL.10 ℃ are reacted 8h down.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:84%.
1H?NMR(300MHz，CDCl 3)δ7.35-7.21(m，5H)，7.08(t，J＝7.8Hz，2H)，6.62(t，J＝7.5Hz，1H)，6.51(d，J＝8.4Hz，2H)，4.22(t，J＝6.6Hz，1H)，4.19-4.00(br?s，1H)，1.88-1.77(m，2H)，0.96(t，J＝7.2Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ147.5，143.9，129.0，128.5，126.8，126.4，117.1，113.2，59.7，31.6，10.8；EI-MS(70V)m/z：211(M +，10.6)，183(14.6)，182(100.0)，104(12.8)，93(7.4)，91(27.2)，77(24.5)，51(6.7).
The asymmetric hydrogenation of embodiment 67:N-phenyl tetralin ketoimine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-phenyl tetralin ketoimine (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:59%.
1H?NMR(300MHz，CDCl 3)δ7.41-7.38(m，1H)，7.23-7.10(m，5H)，6.74-6.67(m，3H)，4.63(t，J＝4.5Hz，1H)，4.89(br?s，1H)，2.88-2.72(m，2H)，2.01-1.75(m，4H)； 13C?NMR(75MHz，CDCl 3)δ147.4，138.1，137.6，129.4，129.2，129.0，127.1，126.1，117.0，112.8，50.9，29.3，28.7，19.4；EI-MS(70V)m/z：223(M +，22.6)，131(100.0)，130(26.1)，129(17.6)，115(14.5)，93(60.4)，91(26.9)，77(14.2).
The asymmetric hydrogenation of embodiment 68:N-(4-p-methoxy-phenyl) tetralone imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-(4-p-methoxy-phenyl) tetralone imines (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:60%.
1H?NMR(300MHz，CDCl 3)δ7.43-7.40(m，1H)，7.20-7.10(m，3H)，6.81(d，J＝8.7Hz，2H)，6.64(d，J＝9.0Hz，2H)，4.55-4.52(m，1H)，3.76(s，3H)，3.60(br?s，1H)，2.87-2.76(m，2H)，1.98-1.76(m，4H)； 13C?NMR(75MHz，CDCl 3)δ151.8，141.7，138.4，137.5，129.2，129.0，127.0，126.0，115.0，114.2，55.8，51.9，29.3，28.6，19.3；EI-MS(70V)m/z：253(M+)，131(100.0)，129(18.6)，123(99.8)，116(14.7)，115(16.9)，108(43.4)，91(32.2).
Embodiment 69: the asymmetric hydrogenation (I) of phenyl-N-(1-phenyl ethylidene) methylamine
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S, 4 ' S)-6e (0.0015mmol); Add substrate phenyl-N-(1-phenyl ethylidene) methylamine (0.15mmol) again; Connect hydrogen balloon, with the air in the hydrogen exchange reaction flask three times, the anhydrous ethylene dichloride of adding 1.5mL.React 12h under the room temperature.Get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:91%.Primary product is (S)
1H?NMR(300MHz，CDCl 3)δ7.36-7.21(m，10H)，3.85-3.78(m，1H)，3.63(q，J＝9.0Hz，2H)，1.37(d，J＝6.5Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ145.5，140.6，128.4，128.3，128.1，126.9，126.7，57.4，51.6，24.5；EI-MS(70V)m/z：211(M +，1.2)，197(9.3)，196(55.5)，105(21.6)，92(8.9)，91(100.0)，77(13.8)，65(9.9).
Embodiment 70: the asymmetric hydrogenation (II) of phenyl-N-(1-phenyl ethylidene) methylamine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6k (0.0015mmol); Add substrate phenyl-N-(1-phenyl ethylidene) methylamine (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:86%.Primary product is (R)
1H?NMR(300MHz，CDCl 3)δ7.36-7.21(m，10H)，3.85-3.78(m，1H)，3.63(q，J＝9.0Hz，2H)，1.37(d，J＝6.5Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ145.5，140.6，128.4，128.3，128.1，126.9，126.7，57.4，51.6，24.5；EI-MS(70V)m/z：211(M +，1.2)，197(9.3)，196(55.5)，105(21.6)，92(8.9)，91(100.0)，77(13.8)，65(9.9).
Embodiment 71: the asymmetric hydrogenation of phenyl-N-(1-(4-p-methoxy-phenyl) ethylidene) methylamine
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free to be handled; (5S, 4 ' S)-6e (0.0015mmol) add substrate phenyl-N-(1-(4-p-methoxy-phenyl) ethylidene) methylamine (0.15mmol) again to add 2.4mg; With the air in the argon replaces reaction flask three times, add the anhydrous ethylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 5bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:90%.
1H?NMR(300MHz，CDCl 3)δ7.34-7.23(m，7H)，6.89(d，J＝8.7Hz，2H)，3.81-3.74(m，4H)，3.62(dd，J＝22.8Hz，13.2Hz，2H)，1.35(d，J＝6.6Hz，3H)； 13CNMR(100MHz，CDCl 3)δ158.5，140.6，137.5，128.3，128.1，127.7，126.8，113.8，56.7，55.2，51.5，24.4.
Embodiment 72: the asymmetric hydrogenation of phenyl-N-(1-(4-aminomethyl phenyl) ethylidene) methylamine
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free to be handled; (5S, 4 ' S)-6e (0.0015mmol) add substrate phenyl-N-(1-(4-aminomethyl phenyl) ethylidene) methylamine (0.15mmol) again to add 2.4mg; With the air in the argon replaces reaction flask three times, add the anhydrous ethylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 5bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:89%.
1H?NMR(300MHz，CDCl 3)δ7.36-7.13(m，9H)，3.78(q，J＝6.3Hz，1H)，3.62(dd，J＝23.7Hz，12.9Hz，2H)，2.35(s，3H)，1.35(d，J＝6.6Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ142.5，140.7，136.5，129.1，128.3，128.1，126.8，126.6，57.1，51.6，24.5，21.1.
Embodiment 73: the asymmetric hydrogenation of phenyl-N-(1-(4-fluorophenyl) ethylidene) methylamine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6e (0.0015mmol); Add substrate phenyl-N-(1-(4-fluorophenyl) ethylidene) methylamine (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 5bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:88%.
1H?NMR(300MHz，CDCl 3)δ7.35-7.22(m，7H)，7.02(t，J＝8.7Hz，2H)，3.80(q，J＝6.3Hz，1H)，3.60(dd，J＝21.6Hz，10.2Hz，2H)，1.34(d，J＝6.3Hz，3H)； 13CNMR(100MHz，CDCl 3)δ142.5，140.7，136.5，129.1，128.3，128.1，126.8，126.6，57.1，51.6，24.5，21.1； 19F?NMR(282MHz，CDCl 3)δ-116.67(s).
Embodiment 74: the asymmetric hydrogenation of phenyl-N-(1-(4-chloro-phenyl-) ethylidene) methylamine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6e (0.0015mmol); Add substrate phenyl-N-(1-(4-chloro-phenyl-) ethylidene) methylamine (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 5bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:91%.
1H?NMR(300MHz，CDCl 3)δ7.36-7.22(m，9H)，3.79(q，J＝6.6Hz，1H)，3.60(dd，J＝22.8Hz，13.2Hz，2H)，1.33(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ144.0，140.3，132.4，128.5，128.4，128.1，128.0，126.9，56.8，51.6，24.5.
Embodiment 75: the asymmetric hydrogenation of phenyl-N-(1-(4-bromophenyl) ethylidene) methylamine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6e (0.0015mmol); Add substrate phenyl-N-(1-(4-bromophenyl) ethylidene) methylamine (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 5bar, react 20h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:89%.
1H?NMR(300MHz，CDCl 3)δ7.48-7.26(m，9H)，3.81-3.54(m，3H)，1.33(d，J＝6.6Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ144.6，140.4，131.5，128.5，128.4，128.1，126.9，126.8，126.7，120.5，56.9，51.6，24.5.
Embodiment 76: the asymmetric hydrogenation of phenyl-N-(1-(2-naphthyl) ethylidene) methylamine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate phenyl-N-(1-(2-naphthyl) ethylidene) methylamine (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:92%.
1H?NMR(400MHz，CDCl 3)δ7.86-7.77(m，4H)，7.55-7.45(m，3H)，7.43-7.22(m，5H)，3.99(q，J＝6.4Hz，1H)，3.66(q，J＝13.2Hz，2H)，1.44(d，J＝6.4Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ142.9，140.5，133.4，132.8，128.3，128.2，128.1，127.7，127.6，126.8，125.9，125.4，125.3，124.8，121.0，57.5，51.6，24.5.
Embodiment 77: the asymmetric hydrogenation of phenyl-N-(1-(6-methoxyl group-2-naphthyl) ethylidene) methylamine
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free to be handled; (5R, 4 ' S)-6e (0.0015mmol) add substrate phenyl-N-(1-(6-methoxyl group-2-naphthyl) ethylidene) methylamine (0.15mmol) again to add 2.4mg; With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:93%.
1H?NMR(400MHz，CDCl 3)δ7.76-7.69(m，3H)，7.49(d，J＝8.1Hz，1H)，7.34-7.21(m，5H)，7.16-7.13(m，2H)，3.98-3.91(m，4H)，3.65(dd，J＝21.3Hz，10.2Hz，2H)，1.43(d，J＝6.6Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ157.4，140.6，133.8，129.2，128.9，128.3，128.1，127.1，126.8，125.4，125.2，118.7，105.6，57.4，55.3，51.6.
The asymmetric hydrogenation of embodiment 78:N-benzyl tetralin ketoimine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-benzyl tetralin ketoimine (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:96%.Primary product is (R).
1H?NMR(300MHz，CHCl 3)δ7.41-7.22(m，7H)，7.17-7.06(m，3H)，4.10-3.80(m，3H)，2.88-2.67(m，2H)，2.08-1.88(m，3H)，1.79-3.66(m，1H)，2.85-2.67(m，2H)，2.50(s，3H)，1.89-1.72(m，4H)ppm； 13C?NMR(100MHz，CHCl 3)δ140.9，139.3，137.4，129.0，128.7，128.3，128.1，126.8，126.6，125.6，54.6，51.1，29.3，28.1，19.0.
The asymmetric hydrogenation of embodiment 79:N-benzyl-6-methoxyl group tetralin ketoimine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-benzyl-6-methoxyl group tetralin ketoimine (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:95%.
1H?NMR(300MHz，CHCl 3)δ7.41-7.21(m，6H)，6.73-6.70(m，1H)，6.61-6.60(m，1H)，3.95-3.74(m，6H)，2.85-2.64(m，2H)，2.05-1.68(m，4H)； 13C?NMR(100MHz，CDCl 3)δ158.1，141.0，138.7，131.7，129.9，128.3，128.1，126.8，113.3，112.0，55.1，54.1，51.0，29.7，28.3，18.9；HRMS-EI(m/z)M +calcd.for?C 18H 21NO?267.1623found?267.1617.
The asymmetric hydrogenation of embodiment 80:N-methyl tetralin ketoimine
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-methyl tetralin ketoimine (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:98%.
1H?NMR(300MHz，CHCl 3)δ7.32-7.10(m，4H)，3.66(m，1H)，2.85-2.67(m，2H)，2.50(s，3H)，1.89-1.72(m，4H)； 13C?NMR(100MHz，CHCl 3)δ139.0，137.3，129.0，128.8，126.6，125.6，57.0，34.0，29.3，27.5，18.7.
The asymmetric hydrogenation of embodiment 81:N-isobutyl-tetralone imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-isobutyl-tetralone imines (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:96%.
1H?NMR(400MHz，CHCl 3)δ7.38-7.05(m，4H)，3.74(t，J＝5.4Hz，1H)，2.84-2.71(m，2H)，2.56-2.45(m，2H)，1.99-1.67(m，5H)，0.98-0.93(m，6H)； 13CNMR(100MHz，CHCl 3)δ139.7，137.4，129.0，128.7，126.5，125.7，55.6，55.4，29.4，28.8，28.3，20.8，20.7，19.0；HRMS-EI(m/z)M +calcd.for?C 14H 21N?203.1674found203.1675.
The asymmetric hydrogenation of embodiment 82:N-benzyl 4-chromanone imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate N-benzyl 4-chromanone imines (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:98%.
1H?NMR(400MHz，CHCl 3)δ7.43-7.32(m，4H)，7.28-7.20(m，2H)，7.16-7.12(m，1H)，6.88-6.80(m，2H)，4.41-4.35(m，1H)，4.24-4.19(m，1H)，3.92(dd，J＝34.8Hz，13.2Hz，2H)，3.83(t，J＝4.0Hz，1H)，2.05-1.99(m，2H)； 13C?NMR(100MHz，CHCl 3)δ154.8，140.5，129.4，128.5，128.4，128.0，127.0，124.6，120.1，116.8，62.5，51.0，50.4，27.4；HRMS-EI(m/z)M +calcd.for?C 16H 17NO?239.1310found?239.1311.
Embodiment 83: the asymmetric hydrogenation (I) of (+/-)-Sertraline imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate (+/-)-Sertraline imines (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency and suitable inverse ratio.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, cis/trans=53: 47, ee of cis isomer 89% (1R, 4R), ee of trans isomer 98% (1R, 4S).
cis?isomer： 1H?NMR(300MHz，CHCl 3)δ7.35(d，J＝8.4Hz，2H)，7.26-7.09(m，3H)，6.98(dd，J＝8.7Hz，1.8Hz，1H)，4.01-3.96(m，1H)，3.74-3.71(m，1H)，2.54(s，3H)，2.09-1.97(m，3H)，1.87-1.81(m，1H)；trans?isomer： 1H?NMR(300MHz，CHCl 3)δ7.45(d，J＝5.4Hz，1H)，7.33(d，J＝6.6Hz，1H)，7.25-7.21(m，1H)，7.15-7.11(m，2H)，6.86-6.82(m，2H)，4.15-4.11(m，1H)，3.78(t，J＝3.9Hz，1H)，2.52(s，3H)，2.39-2.32(m，1H)，1.99-1.92(m，1H)，1.78-1.72(m，2H).
Embodiment 84: the asymmetric hydrogenation (II) of (+/-)-Sertraline imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6e (0.0015mmol); Add substrate (+/-)-Sertraline imines (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency and suitable inverse ratio.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, cis/trans=95: 5, ee of cis isomer 3% (1S, 4S), ee of trans isomer 68% (1S, 4R).
cis?isomer： 1H?NMR(300MHz，CHCl 3)δ7.35(d，J＝8.4Hz，2H)，7.26-7.09(m，3H)，6.98(dd，J＝8.7Hz，1.8Hz，1H)，4.01-3.96(m，1H)，3.74-3.71(m，1H)，2.54(s，3H)，2.09-1.97(m，3H)，1.87-1.81(m，1H)；trans?isomer： 1H?NMR(300MHz，CHCl 3)δ7.45(d，J＝5.4Hz，1H)，7.33(d，J＝6.6Hz，1H)，7.25-7.21(m，1H)，7.15-7.11(m，2H)，6.86-6.82(m，2H)，4.15-4.11(m，1H)，3.78(t，J＝3.9Hz，1H)，2.52(s，3H)，2.39-2.32(m，1H)，1.99-1.92(m，1H)，1.78-1.72(m，2H).
Embodiment 85: (R)-and the asymmetric hydrogenation (I) of Sertraline imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate (R)-Sertraline imines (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency and suitable inverse ratio.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, cis/trans=97: 3, ee of cis isomer＞99% (1R, 4R), ee of trans isomer＞99% (1S, 4R).
cis?isomer： 1H?NMR(300MHz，CHCl 3)δ7.35(d，J＝8.4Hz，2H)，7.26-7.09(m，3H)，6.98(dd，J＝8.7Hz，1.8Hz，1H)，4.01-3.96(m，1H)，3.74-3.71(m，1H)，2.54(s，3H)，2.09-1.97(m，3H)，1.87-1.81(m，1H)；trans?isomer： 1H?NMR(300MHz，CHCl 3)δ7.45(d，J＝5.4Hz，1H)，7.33(d，J＝6.6Hz，1H)，7.25-7.21(m，1H)，7.15-7.11(m，2H)，6.86-6.82(m，2H)，4.15-4.11(m，1H)，3.78(t，J＝3.9Hz，1H)，2.52(s，3H)，2.39-2.32(m，1H)，1.99-1.92(m，1H)，1.78-1.72(m，2H).
Embodiment 86: (R)-and the asymmetric hydrogenation (II) of Sertraline imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6e (0.0015mmol); Add substrate (R)-Sertraline imines (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency and suitable inverse ratio.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency: 91%, cis/trans=91: 9, ee of cis isomer＞99% (1R, 4R), ee of trans isomer＞99% (1S, 4R).
cis?isomer： 1H?NMR(300MHz，CHCl 3)δ7.35(d，J＝8.4Hz，2H)，7.26-7.09(m，3H)，6.98(dd，J＝8.7Hz，1.8Hz，1H)，4.01-3.96(m，1H)，3.74-3.71(m，1H)，2.54(s，3H)，2.09-1.97(m，3H)，1.87-1.81(m，1H)；trans?isomer： 1H?NMR(300MHz，CHCl 3)δ7.45(d，J＝5.4Hz，1H)，7.33(d，J＝6.6Hz，1H)，7.25-7.21(m，1H)，7.15-7.11(m，2H)，6.86-6.82(m，2H)，4.15-4.11(m，1H)，3.78(t，J＝3.9Hz，1H)，2.52(s，3H)，2.39-2.32(m，1H)，1.99-1.92(m，1H)，1.78-1.72(m，2H).
Embodiment 87: (S)-and the asymmetric hydrogenation (I) of Sertraline imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate (S)-Sertraline imines (0.15mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency and suitable inverse ratio.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, cis/trans=5: 95, ee of cis isomer＞99% (1S, 4S), ee of trans isomer＞99% (1R, 4S).
cis?isomer： 1H?NMR(300MHz，CHCl 3)δ7.35(d，J＝8.4Hz，2H)，7.26-7.09(m，3H)，6.98(dd，J＝8.7Hz，1.8Hz，1H)，4.01-3.96(m，1H)，3.74-3.71(m，1H)，2.54(s，3H)，2.09-1.97(m，3H)，1.87-1.81(m，1H)；trans?isomer： 1H?NMR(300MHz，CHCl 3)δ7.45(d，J＝5.4Hz，1H)，7.33(d，J＝6.6Hz，1H)，7.25-7.21(m，1H)，7.15-7.11(m，2H)，6.86-6.82(m，2H)，4.15-4.11(m，1H)，3.78(t，J＝3.9Hz，1H)，2.52(s，3H)，2.39-2.32(m，1H)，1.99-1.92(m，1H)，1.78-1.72(m，2H).
Embodiment 88: (S)-and the asymmetric hydrogenation (II) of Sertraline imines
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6e (0.0015mmol); Add substrate (S)-Sertraline imines (0.15mmol) again,, add the anhydrous ethylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 12h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency and suitable inverse ratio.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, cis/trans=＞99/1, ee of cis isomer＞99% (1S, 4S), ee of trans isomer＞99% (1R, 4S).
cis?isomer： 1H?NMR(300MHz，CHCl 3)δ7.35(d，J＝8.4Hz，2H)，7.26-7.09(m，3H)，6.98(dd，J＝8.7Hz，1.8Hz，1H)，4.01-3.96(m，1H)，3.74-3.71(m，1H)，2.54(s，3H)，2.09-1.97(m，3H)，1.87-1.81(m，1H).
Embodiment 89: (E)-1, and the asymmetric hydrogenation (I) of 2-phenylbenzene-1-propylene
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol) adds substrate (E)-1 again, 2-phenylbenzene-1-propylene (0.15mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:96%.Primary product is (R).
1H?NMR(400MHz，CDCl 3)δ7.30-7.07(m，10H)，3.02-2.92(m，2H)，2.79-2.74(m，1H)，1.24(d，J＝6.8Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ147.0，140.8，129.1，128.3，128.1，127.0，126.0，125.8，45.0，41.8，21.1；EI-MS(70V)m/z：196(M +，9.2)，106(9.3)，105(100.0)，104(16.6)，103(7.6)，91(14.6)，79(8.8)，77(12.4).
Embodiment 90: (E)-1, and the asymmetric hydrogenation (II) of 2-phenylbenzene-1-propylene
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol) adds 1.46g substrate (E)-1 again, 2-phenylbenzene-1-propylene (7.5mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 3mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:96%.Primary product is (R).
1H?NMR(400MHz，CDCl 3)δ7.30-7.07(m，10H)，3.02-2.92(m，2H)，2.79-2.74(m，1H)，1.24(d，J＝6.8Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ147.0，140.8，129.1，128.3，128.1，127.0，126.0，125.8，45.0，41.8，21.1；EI-MS(70V)m/z：196(M +，9.2)，106(9.3)，105(100.0)，104(16.6)，103(7.6)，91(14.6)，79(8.8)，77(12.4).
Embodiment 91: (E)-and the asymmetric hydrogenation of 2-(4-p-methoxy-phenyl)-1-phenyl-1-propylene
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free to be handled; (5R, 4 ' S)-6e (0.0015mmol) add 1.46g substrate (E)-2-(4-p-methoxy-phenyl)-1-phenyl-1-propylene (0.15mmol) again to add 2.4mg; With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:97%.
1H?NMR(300MHz，CDCl 3)δ7.23-7.06(m，7H)，6.84-6.80(m，2H)，3.79(s，3H)，2.97-2.86(m，2H)，2.77-2.73(m，1H)，1.21(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ157.7，140.9，139.0，129.1，128.0，127.8，125.7，113.6，55.1，45.2，41.0，21.3；EI-MS(70V)m/z：226(M +，3.1)，136(10.0)，135(100.0)，105(9.6)，103(6.0)，91(12.7)，79(4.6)，77(5.8)，65(5.3).
Embodiment 92: (E)-and the asymmetric hydrogenation of 2-(4-chloro-phenyl-)-1-phenyl-1-propylene
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); ((E)-2-(4-chloro-phenyl-)-1-phenyl-1-propylene (0.015mmol) with the air in the argon replaces reaction flask three times, adds the anhydrous methylene dichloride of 1.5mL to add substrate again.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:96%.
1H?NMR(300MHz，CDCl 3)δ7.25-7.03(m，9H)，3.02-2.73(m，3H)，1.23(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ145.2，140.3，131.5，129.1，128.4，128.3，128.1，125.9，44.9，41.3，21.2；EI-MS(70V)m/z：232(M ++2，1.9)，230(M +，5.7)，141(31.6)，140(12.3)，139(100.0)，138(11.4)，103(35.4)，91(18.1)，77(17.3)，65(8.1).
Embodiment 93: (E)-and the asymmetric hydrogenation of Beta-methyl ETHYL CINNAMATE
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6f (0.0015mmol); Add substrate (E)-Beta-methyl ETHYL CINNAMATE (0.015mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:98%.Primary product is (R).
1H?NMR(300MHz，CDCl 3)δ.7.33-7.18(m，5H)，4.08(q，J＝7.2Hz，2H)，3.31-3.24(m，1H)，2.65-2.49(m，2H)，1.30(d，J＝6.9Hz，3H)，1.18(t，J＝7.2Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ172.4，145.7，128.5，126.8，126.4，60.3，43.0，36.5，21.8，14.2；EI-MS(70V)m/z：192(M+，23.8)，121(33.6)，118(80.0)，117(15.7)，105(100.0)，103(14.3)，91(20.4)，77(18.6).
Embodiment 94: (E)-and the asymmetric hydrogenation of 3-(4-p-methoxy-phenyl)-2-butylene acetoacetic ester
In argon gas atmosphere; Reaction flask is carried out anhydrous and oxygen-free to be handled; (5R, 4 ' S)-6f (0.0015mmol) add substrate (E)-3-(4-p-methoxy-phenyl)-2-butylene acetoacetic ester (0.015mmol) again to add 2.4mg; With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:97%.
1H?NMR(300MHz，CDCl 3)δ7.15(dd，J＝9.3Hz，2.4Hz，2H)，6.86-6.81(m，2H)，4.07(q，J＝7.2Hz，2H)，3.78(s，3H)，3.27-3.20(m，1H)，2.61-2.46(m，2H)，1.27(d，J＝7.2Hz，3H)，1.18(t，J＝7.2Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ172.4，158.0，137.8，127.6，113.7，60.2，55.2，43.2，35.7，21.9，14.1；EI-MS(70V)m/z：222(M +，13.7)，148(10.1)，136(10.2)，135(100.0)，134(5.9)，105(6.6)，91(8.0)，77(5.3).
Embodiment 95: (E)-and the asymmetric hydrogenation of 3-(4-chloro-phenyl-)-2-butylene acetoacetic ester
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6a (0.0015mmol); Add substrate (E)-3-(4-chloro-phenyl-)-2-butylene acetoacetic ester (0.015mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:97%.
1H?NMR(300MHz，CDCl 3)δ7.28-7.25(m，2H)，7.16(d，J＝8.4Hz，2H)，4.07(q，J＝7.5Hz，2H)，3.29-3.22(m，1H)，2.61-2.48(m，2H)，1.28(d，J＝7.2Hz，3H)，1.18(t，J＝7.8Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ172.0，144.1，132.0，128.5，128.1，60.3，42.8，35.9，21.8，14.1；EI-MS(70V)m/z：228(M ++2，6.8)，226(M +，20.4)，155(36.5)，154(20.9)，152(63.8)，141(34.0)，139(100.0)，103(37.8)，77(18.1).
Embodiment 96:1-methyl-6-methoxyl group-3, the asymmetric hydrogenation of 4-dihydronaphthalene (I)
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6a (0.0015mmol) adds substrate 1-methyl-6-methoxyl group-3 again, 4-dihydronaphthalene (0.015mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:90%.
1H?NMR(300MHz，CDCl 3)δ7.12(d，J＝9.0Hz，1H)，6.71(dd，J＝8.4Hz，2.4Hz，1H)，6.60(d，J＝2.7Hz，1H)，3.77(s，3H)，2.86-2.73(m，3H)，1.93-1.69(m，2H)，1.56-1.48(m，1H)，1.25(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ157.1，138.0，134.3，129.0，113.3，111.8，55.1，31.7，31.6，30.3，22.9，20.4；EI-MS(70V)m/z：176(M +，23.0)，162(12.5)，161(100.0)，139(25.9)，115(12.7)，103(14.4)，91(18.2)，77(11.5).
Embodiment 97:1-methyl-6-methoxyl group-3, the asymmetric hydrogenation of 4-dihydronaphthalene (II)
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6d (0.0015mmol) adds substrate 1-methyl-6-methoxyl group-3 again, 4-dihydronaphthalene (0.015mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 0.75mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:87%.
1H?NMR(300MHz，CDCl 3)δ7.12(d，J＝9.0Hz，1H)，6.71(dd，J＝8.4Hz，2.4Hz，1H)，6.60(d，J＝2.7Hz，1H)，3.77(s，3H)，2.86-2.73(m，3H)，1.93-1.69(m，2H)，1.56-1.48(m，1H)，1.25(d，J＝6.9Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ157.1，138.0，134.3，129.0，113.3，111.8，55.1，31.7，31.6，30.3，22.9，20.4；EI-MS(70V)m/z：176(M +，23.0)，162(12.5)，161(100.0)，139(25.9)，115(12.7)，103(14.4)，91(18.2)，77(11.5).
Embodiment 98:1-methyl-3, the asymmetric hydrogenation of 4-dihydronaphthalene (I)
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6a (0.0015mmol) adds substrate 1-methyl-3 again, 4-dihydronaphthalene (0.015mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:88%.
1H?NMR(300MHz，CDCl 3)δ7.22-7.05(m，4H)，2.94-2.62(m，3H)，1.95-1.68(m，3H)； 13C?NMR(75MHz，CDCl 3)δ142.1，136.8，129.0，128.1，125.6，125.4，32.4，31.4，29.9，22.9，20.4；EI-MS(70V)m/z：147(M ++1，100.0)，146(M +，20.0)，145(54.9)，144(45.6)，129(72.9)，128(33.7)，118(32.6)，115(36.1)，91(65.8).
Embodiment 99:1-methyl-3, the asymmetric hydrogenation of 4-dihydronaphthalene (II)
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6d (0.0015mmol) adds substrate 1-methyl-3 again, 4-dihydronaphthalene (0.015mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 0.75mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:85%.
1H?NMR(300MHz，CDCl 3)δ7.22-7.05(m，4H)，2.94-2.62(m，3H)，1.95-1.68(m，3H)； 13C?NMR(75MHz，CDCl 3)δ142.1，136.8，129.0，128.1，125.6，125.4，32.4，31.4，29.9，22.9，20.4；EI-MS(70V)m/z：147(M ++1，100.0)，146(M +，20.0)，145(54.9)，144(45.6)，129(72.9)，128(33.7)，118(32.6)，115(36.1)，91(65.8).
Embodiment 100:1-phenyl-6-methoxyl group-3, the asymmetric hydrogenation of 4-dihydronaphthalene
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6a (0.0015mmol) adds substrate 1-phenyl-6-methoxyl group-3 again, 4-dihydronaphthalene (0.015mmol); With the air in the argon replaces reaction flask three times, add the anhydrous methylene dichloride of 1.5mL.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:91%.
1H?NMR(300MHz，CDCl 3)δ7.30-7.08(m，5H)，6.76-6.73(m，1H)，6.66-6.60(m，2H)，4.05(t，J＝6.3Hz，1H)，3.78(s，3H)，2.93-2.76(m，2H)，2.18-2.09(m，1H)，1.93-1.68(m，3H)； 13C?NMR(75MHz，CDCl 3)δ157.6，147.7，138.7，131.6，131.1，128.7，128.2，125.9，113.2，112.0，55.1，44.9，33.4，30.1，20.9；EI-MS(70V)m/z：239(M ++1，36.4)，238(M +，100.0)，210(64)，209(36.4)，179(18.5)，178(15.7)，91(36.6).
Embodiment 101: (Z)-and the asymmetric hydrogenation (I) of 3-methyl-5-phenyl-2-allyl acetic acid ethyl ester
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6i (0.0015mmol); Add substrate (Z)-3-methyl-5-phenyl-2-allyl acetic acid ethyl ester (0.015mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:85%.Primary product is (R).
1H?NMR(300MHz，CDCl 3)δ7.30-7.26(m，2H)，7.19-7.13(m，3H)，4.20(q，J＝7.2Hz，2H)，2.68-2.55(m，2H)，2.35(dd，J＝14.7Hz，6.0Hz，1H)，2.20-2.12(m，1H)，2.06-1.99(m，1H)，1.71-1.63(m，1H)，1.57-1.48(m，1H)，1.25(t，J＝6.9Hz，3H)，1.01(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ173.0，142.3，128.3，128.2，125.7，60.1，41.7，38.5，33.3，30.1，19.6，14.2；EI-MS(70V)m/z：220(M +，3.7)，175(26.9)，174(68.3)，131(30.3)，115(17.0)，104(23.9)，92(23.4)，91(100.0)，88(28.2).
Embodiment 102: (Z)-and the asymmetric hydrogenation (II) of 3-methyl-5-phenyl-2-allyl acetic acid ethyl ester
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6h (0.0015mmol); Add substrate (Z)-3-methyl-5-phenyl-2-allyl acetic acid ethyl ester (0.015mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:85%.Primary product is (R).
1H?NMR(300MHz，CDCl 3)δ7.30-7.26(m，2H)，7.19-7.13(m，3H)，4.20(q，J＝7.2Hz，2H)，2.68-2.55(m，2H)，2.35(dd，J＝14.7Hz，6.0Hz，1H)，2.20-2.12(m，1H)，2.06-1.99(m，1H)，1.71-1.63(m，1H)，1.57-1.48(m，1H)，1.25(t，J＝6.9Hz，3H)，1.01(d，J＝6.6Hz，3H)； 13C?NMR(75MHz，CDCl 3)δ173.0，142.3，128.3，128.2，125.7，60.1，41.7，38.5，33.3，30.1，19.6，14.2；EI-MS(70V)m/z：220(M +，3.7)，175(26.9)，174(68.3)，131(30.3)，115(17.0)，104(23.9)，92(23.4)，91(100.0)，88(28.2).
Embodiment 103: (E)-and the asymmetric hydrogenation (I) of 3-methyl-4-phenyl-3-butene-2-ketone
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6b (0.0015mmol); Add substrate (E)-3-methyl-4-phenyl-3-butene-2-ketone (0.015mmol) again,, add the anhydrous toluene of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:98%.Primary product is (S).
1H?NMR(300MHz，CDCl 3)δ7.31-7.14(m，5H)，3.03-2.97(m，1H)，2.87-2.80(m，1H)，2.60-2.53(m，1H)，2.09(s，3H)，1.09(d，J＝6.9Hz，3H).
Embodiment 104: (E)-and the asymmetric hydrogenation (II) of 3-methyl-4-phenyl-3-butene-2-ketone
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5S; 4 ' S)-6a (0.0015mmol); Add substrate (E)-3-methyl-4-phenyl-3-butene-2-ketone (0.015mmol) again,, add the anhydrous methylene dichloride of 1.5mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 20bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:97%.Primary product is (R).
1H?NMR(300MHz，CDCl 3)δ7.31-7.14(m，5H)，3.03-2.97(m，1H)，2.87-2.80(m，1H)，2.60-2.53(m，1H)，2.09(s，3H)，1.09(d，J＝6.9Hz，3H).
The asymmetric hydrogenation (I) of embodiment 105:2-(4-p-methoxy-phenyl)-3-methyl-2-butene
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6a (0.0015mmol); Add substrate 2-(4-p-methoxy-phenyl)-3-methyl-2-butene (0.015mmol) again,, add the anhydrous methylene dichloride of 0.75mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 50bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:58%.
1H?NMR(300MHz，CDCl 3)δ7.07(d，J＝8.1Hz，2H)，6.82(d，J＝7.8Hz，2H)，3.79(s，3H)，2.40-2.36(m，1H)，1.75-1.68(m，1H)，1.20(d，J＝7.5Hz，3H)，0.91(d，J＝6.6Hz，3H)，0.74(d，J＝6.9Hz，3H)；EI-MS(70V)m/z：178(M +，9.4)，136(10.3)，135(100.0)，105(12.6)，103(6.0)，91(8.7)，77(6.1)，58(65.4).
The asymmetric hydrogenation (II) of embodiment 106:2-(4-p-methoxy-phenyl)-3-methyl-2-butene
In argon gas atmosphere, reaction flask is carried out anhydrous and oxygen-free handle, add 2.4mg (5R; 4 ' S)-6e (0.0015mmol); Add substrate 2-(4-p-methoxy-phenyl)-3-methyl-2-butene (0.015mmol) again,, add the anhydrous methylene dichloride of 0.75mL with the air in the argon replaces reaction flask three times.In glove box, open reaction flask,, the reaction flask of having filled in bottleneck is transferred in the autoclave, take out autoclave, use H with the good bottleneck of plastics Nei Saisai that has an aperture 2Replace three times, charge into H 2To 100bar, react 2h under the room temperature.In stink cupboard, carefully bleed off reactant gases, get partial reaction liquid and take out and desolvate, use 1H NMR measures transformation efficiency.Resistates is measured enantioselectivity through HPLC after crossing a silica gel short column.Transformation efficiency:＞99%, ee:60%.
1H?NMR(300MHz，CDCl 3)δ7.07(d，J＝8.1Hz，2H)，6.82(d，J＝7.8Hz，2H)，3.79(s，3H)，2.40-2.36(m，1H)，1.75-1.68(m，1H)，1.20(d，J＝7.5Hz，3H)，0.91(d，J＝6.6Hz，3H)，0.74(d，J＝6.9Hz，3H)；EI-MS(70V)m/z：178(M +，9.4)，136(10.3)，135(100.0)，105(12.6)，103(6.0)，91(8.7)，77(6.1)，58(65.4).

Claims (9)

1. volution skeleton phosphine oxazoline part is characterized in that having following general structure:
Figure FSB00000744331100011
R in the formula 3=phenyl, Ar=phenyl or R 3=benzyl, Ar=o-Tol.
2. the preparation method of a volution skeleton phosphine oxazoline part, described volution skeleton phosphine oxazoline part has following general structure:
Figure FSB00000744331100012
The integer of n=0-3 in the formula; R 1, R 2Be selected from hydrogen, C respectively 1-6Alkyl, R xOr/and R x' substituted phenyl;
R 3=C 1-6Alkyl or benzyl;
Ar=R xOr/and R x" substituted phenyl or 2-furyl;
Described R x, R x' be selected from hydrogen, C respectively 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Perfluoroalkyl, C 5-7Naphthenic base, phenyl, benzyl, 1-phenylethyl, 1-naphthyl, 2-naphthyl or halogen;
It is characterized in that following steps (1)～(2):
(1) compound 3 ' obtain with two trifluoro-methylsulfonyl anilines reactions (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (5S, the compound 4 of 4 ' R) configurations ';
(2) compound 4 ' with Ar 2PH reacts in the presence of catalyzer and obtains target ligand, promptly described ((5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (5S, the compound 5 of 4 ' R) configurations ';
Said compound 3 ' can be (5S, 4 ' S) or (5R, 4 ' S) or (5S, 4 ' R) or (its structure is following for 5R, 4 ' R) configurations:
Figure FSB00000744331100021
Described compound 4 ' can be (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (its structure is following for 5S, 4 ' R) configurations:
Figure FSB00000744331100022
OTf is a trifyl in the formula.
Described compound 5 ' can be (5R, 4 ' S) or (5S, 4 ' S) or (5R, 4 ' R) or (its structure is following for 5S, 4 ' R) configurations:
Figure FSB00000744331100023
R in the said structure 1, R 2, R 3, Ar and n as previously mentioned.
3. method as claimed in claim 2 is characterized in that described n=1, R 1=R 2=H, described compound 3 ', 4 ' and 5 ' has following structural formula:
Figure FSB00000744331100031
R in the formula 3, Ar such as claim 2 be said, OTf is a trifyl.
4. method as claimed in claim 3 is characterized in that:
Described step (1) is under rare gas element, in the organic solvent, (5R, 4 ' S) or (5S, the compound 3 of 4 ' S) configurations and two trifluoro-methylsulfonyl aniline (PhNTf 2) and alkali reaction, obtain (5S, 4 ' S) or (5R, the compound 4 of 4 ' S) configurations; Wherein the mol ratio of compound 3, two trifluoro-methylsulfonyl anilines and alkali is 1: 1-2: 1-2, and temperature of reaction :-78 ℃-100 ℃, the reaction times: 1-48h;
Described step (2) is under rare gas element, in the organic solvent, (5S, 4 ' S) or (5R, the compound 4 and the diaryl phosphine hydrogen Ar of 4 ' S) configurations 2PH is at palladium catalyst and triphenylphosphine, 1,2-two (diphenylphosphino) ethane, 1, and 3-two (diphenylphosphino) propane or 1,4-two (diphenylphosphino) butane part reacts under existing, and obtains (5S, 4 ' S) or (5R, the compound 5 of 4 ' S) configurations respectively; Wherein compound 4 and Ar 2The mol ratio of PH is 1: 1-5, described Ar 2The Ar of PH according to claim 1; Palladium catalyst is Pd (PPh 3) 4, Pd (dba) 2, Pd 2(dba) 3, Pd 2(dba) 3CHCl 3Or Pd (0Ac) 2, the consumption of palladium catalyst is the 0.1-50% of compound 4, temperature of reaction: 0 ℃-150 ℃, and the reaction times: 1-48h; Described dba is a dibenzalacetone.
5. iridium complex, it is characterized in that described iridium complex be compound 6 with following structural formula ':
Figure FSB00000744331100032
N=1 in the formula, R 1, R 2=H, R 3=phenyl, Ar=phenyl or R 3=benzyl, Ar=o-Tol;
X is hexafluoro-phosphate radical, hexafluoro tellurate radical, tetrafluoroborate, tetraphenyl borate or four-(3,5-two trifluoromethyls) borate.
6. an iridium complex as claimed in claim 5 is characterized in that described iridium complex is by the described part of claim 1 and [Ir (cod) Cl] 2With NaX in organic medium, react obtain iridium complex 6 '; Wherein part, [Ir (cod) Cl] 2With the mol ratio of NaX be 2-100: 1: 1-5, temperature of reaction: 0 ℃-100 ℃, the reaction times: 1-20h; Described cod is 1, the 5-cyclooctadiene.
7. the application of an iridium complex, described iridium complex such as claim 5 are said, it is characterized in that being used to prepare chirality asymmetric hydrogenation product.
8. application as claimed in claim 7 is characterized in that at least a described part of claim 1 and [Ir (cod) Cl] of being selected from 2The complex compound 6 that generates ' catalysis under, imines and alkene and H 2Asymmetric hydrogenation takes place; Described imines is the imines of ring-type or non-annularity ketone and aromatic amine or amine compound formation; Described alkene is that ring-type or acyclic two replaces or three replacement or the quaternary substituted alkene of one or more aromatic rings or alpha, beta-unsaturated esters compound or the alpha, beta-unsaturated ketone compounds of having, and described cod is 1, the 5-cyclooctadiene.
9. application as claimed in claim 8, it is characterized in that described imines or alkene, iridium catalyst 6 ' mol ratio be 100-5000: 1, temperature of reaction: 0 ℃-120 ℃, reaction times: 0.1-100h, described H 2Pressure: 0.5-100 normal atmosphere.
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