CN108707144A - A kind of chirality quinoline amine compounds and its preparation method and application - Google Patents

A kind of chirality quinoline amine compounds and its preparation method and application Download PDF

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CN108707144A
CN108707144A CN201810207559.XA CN201810207559A CN108707144A CN 108707144 A CN108707144 A CN 108707144A CN 201810207559 A CN201810207559 A CN 201810207559A CN 108707144 A CN108707144 A CN 108707144A
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quinoline
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陆展
陈旭
程朝阳
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Zhejiang University ZJU
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Abstract

The invention discloses chiral quinoline amine compounds shown in a kind of formula (1), and disclose a kind of preparation method of simplicity.Quinoline amine compounds can be used for preparing chiral organic boron ester compounds shown in formula (1) provided by the invention.Chiral oxazoline or imidazoline phenylchinoline amine compounds provided by the invention and transition metal M Y 'nComplexes ira situ object can be used as homogeneous catalyst, catalyst is used to prepare chiral organoboron compound by carrying out the addition of asymmetric reduction in the carbon carbon atom double bond of prochiral organic compounds, and it is styrene compound to act on preferred prochirality unsaturated compound for asymmetric reduction.Can chiral organic boron ester compounds prepared in accordance with the present invention be a kind of important organic synthesis intermediate, especially pharmaceutical preparation, fragrance and fumet, agricultural chemicals production in terms of.

Description

A kind of chirality quinoline amine compounds and its preparation method and application
Technical field
The present invention relates to a kind of chiral quinoline amine compounds and its preparation method and application, and in particular to synthesis Evil containing hand Oxazoline or imidazoline or thiazoline phenylchinoline amine compounds and preparation method thereof and the chipal compounds are urged altogether with cobalt or iron Change the purposes in the asymmetric geneva hydroboration of aromatic olefin.
Background technology
Chiral benzyl position boron ester is a kind of important He Chengzhongjianti [C.Sandford,V.K.Aggarwal,Chem. Commun.2017,53,5481.], the asymmetric hydroboration of alkene is a kind of high-efficient simple for preparing chiral benzyl position boron ester Method, it is high with reaction of atomic economy to have many advantages, such as that raw material is easy to get, receive synthesis chemist extensive concern.
1989, Hayashi and Ito et al. were using chirality BINAP ligand Ls 1, in the styrene compound that Rh is catalyzed Made breakthrough progress in asymmetric hydroboration, product ee values are up to 96%, but the reaction used it is unstable Catecholborane reagent and unstable products, while needing the carry out &#91 under -78 DEG C of low temperature;T.Hayashi,Y.Matsumoto, Y.Ito,J.Am.Chem.Soc.1989,111,3426].1993, Brown groups were realized using chiral P, N ligand Ls 2 The asymmetric geneva hydroboration of the styrene and catecholborane of Rh catalysis, the ee values of reaction are up to 88% [J.M.Brown,D.I.Hulmes,T. P.Layzell,J.Chem.Soc.Chem.Commun.1993,1673.].Nineteen ninety-five, The small chiral ferrocene ligands L3 being combined into containing pyrrole ring of Togni apply it to the styrene and catechol of Rh catalysis Borine
In asymmetric hydroboration, it can be worth to chiral boron to be up to 98% ee, but the regioselectivity reacted The ratio of difference, geneva product and anti-geneva product compares 2&#91 for 3;A.Schnyder,L.Hintermann,A. Togni, Angew.Chem.,Int.Ed.1995,34,931.].2001, Knochel et al. reported a kind of novel biphosphine ligand L4 Synthetic method, and use it for Rh catalysis styrene compound asymmetric hydroboration in, product ee value highests Up to 93%[S.Demay,F.Volant,P.Knochel,Angew. Chem.,Int.Ed.2001,40,1235.].2002 Year, Schmalz groups apply to biphosphine ligand L5 in the asymmetric hydroboration of the styrene of Rh catalysis, the ee of product Value is 88%, and yield is up to 97%[F. Blume,S.Zemolka,T.Fey,R.Kranich,H.G.Schmalz, Adv.Synth.Catal.2002,344, 868.].2004, Crudden et al. realized the benzene of Rh catalysis using ligand L 6 In ethylene and the asymmetric hydroboration of HBPin, reaction ee is up to 88%, obtains stable chiral boron ester products, still Regioselectivity compare Cha [C.M.Crudden,Y.B.Hleba,A.C.Chen,J.Am.Chem.Soc.2004,126, 9200.]. 2015, group of Tang Wen armies used Phosphine ligands L7, was homing device using amide on substrate, realized the positions the α acetyl of Rh catalysis The styrene substrate asymmetry geneva boronation reaction of amido substitution, generates corresponding chiral quaternary carbon boron compound, and ee values are up to 96%[N.F.Hu,G.Q.Zhao,Y.Y.Zhang,X.Q.Liu, G.Y.Li,W.J.Tang,J.Am.Chem.Soc.2015, 137,6746.].2009, Yun groups use chiral phosphine ligand 5-8, realize copper catalysis the high region of phenylethylene substrate and The asymmetric geneva hydroboration (51-95%ee) of stereoselectivity, but the narrow range of functional group compatibility (only reported Fluorine, chlorine, methoxyl group and methyl substituted styrene substrate) [D.Noh,H.Chea,J.Ju,J.Yun, Angew.Chem.Int.Ed. 2009,48,6062].Later, it is right using the 5-9 ligands of big steric hindrance to realize copper catalysis height for they The geneva hydroboration of 1, the 2- di-substituted aryl perfume (or spice) alkene of body selectivity is reflected, reaction only reports 6 examples, and on phenyl ring The substrate Wei Jianbaodao &#91 of substituted base;D.Noh,S.K.Yoon,J.Won,J.Y.Lee,J.Yun,Chem. Asian J.2011, 6,1967.].It is difficult to prepare and the chiral phosphine ligand of air-sensitive in addition, having used in the two examples.
From the above summary it is found that realizing phenylethylene to a certain extent using noble metal catalyst and cheap metal copper The geneva hydroboration (Scheme 1) in object high region and enantio-selectivity, but still having some limitations property are closed, it is such as big It is boron source that the catecholborane of air-sensitive is used in partial example, corresponding chirality boron unstable products, with alcohol after aerobicization Form separation；Reaction needs to carry out under low temperature；Using metastable HBPin be boron source when, the regioselectivity of reaction is poor； The ligand used in most of reaction is chiral phosphine ligand (Scheme 2).These factors limit alkene asymmetry geneva boron Application of the hydrogenation in the boron ester of synthesis of chiral benzyl position.
Earth high yield metallic iron and cobalt are cheap, and toxicity is relatively low and environmental-friendly, are obtained in asymmetric catalysis field Extensive Guan Zhu [H.Pellissier,H.Clavier,Chem.Rev.2014,114,2775；K. Gopalaiah, Chem.Rev.2013,113,3248.].Over nearest 5 years, the alkene asymmetric hydroboration of iron and cobalt catalysis achieves one Fixed Jin Zhan [L.Zhang,Z.Zuo,X.Wan,Z.Huang,J.Am.Chem. Soc.,2014,136,15501.； J.H.Chen,T.Xi,X.Ren,B.Cheng,J.Guo,Z.Lu,Org. Chem.Front.2014,1,1306；J.H.Chen, T.Xi,Z.Lu,Org.Lett.2014,16,6452；H.Y. Zhang,Z.Lu,ACS Catal.2016,6,6596； C.H.Chen,X.Z.Shen,J.H.Chen,X.Hong, Z.Lu,Org.Lett.2017,19,5422.].It is reported from these In example, we can see that 1, in the anti-geneva asymmetric hydroboration of 1- disubstituted olefins, earth high yield transition gold Belonging to iron and cobalt can largely match in excellence or beauty noble metal catalyst.But the styrene up to the present, being catalyzed for iron or cobalt Asymmetric geneva hydroboration research with 1,2- di-substituted aryl perfume (or spice) alkene there is no literature reported on.
From the angle of sustainable development and Green Chemistry, if we can develop simplicity be easily-synthesized and be suitable for iron, Earth high yield transition metal iron and cobalt are substituted noble metal catalyst and apply the geneva in aromatic olefin not right by the chiral ligand of cobalt Claim in hydroboration, while solving the deficiency in the conversion of existing precious metal catalyst and copper catalysis, then has very important Theory and practice meaning.
Invention content
The invention discloses a kind of novel containing chiral oxazoline or imidazoline or thiazoline phenylchinoline amine compounds And preparation method thereof and these compounds and iron, cobalt be total to catalytic applications in asymmetric syntheses, especially phenylethylene chemical combination In the asymmetric geneva hydroboration of object, and the asymmetric geneva boron hydrogen of cheap metal iron catalysis aromatic olefin is realized for the first time Change reaction.
The present invention is achieved through the following technical solutions：
In a first aspect, quinoline amine compounds shown in a kind of formula (1) of present invention offer,
In formula (1), X O, S or NR14；
R1, R2, R3, R4, R5, R6, R7, R8, R9And R10Respectively stand alone as the fluorine of hydrogen, halogen, the alkyl of C1-C10, C1-C4 The aryl of alkyl, the alkoxy of C1-C4, the naphthenic base of C3~C10 or C6-C14；
R11With R12Respectively stand alone as the aryl of hydrogen, the alkyl of C1-C10 or C6-C14；
R13For the alkyl of C1-C12, the aryl of the naphthenic base of C3~C12, benzyl or C6-C14, the wherein alkyl of C1-C12 On H it is not substituted or replaced by the alkoxy of 1-2 C1-C4；H in the naphthenic base of the C3~C12 it is not substituted or by The alkoxy of 1-3 C1-C4 alkyl or C1-C4 replace, and the H on the aryl of the C6-C14 is unsubstituted or is replaced by 1-3 Base A substitution, the substituent A be the alkyl of C1-C4, the alkoxy of C1-C4, the fluoroalkyl of C1-C4, C1-C4 Fluoroalkyloxy, F or Cl；
R14For hydrogen, the aryl of the alkyl of C1-C10, benzyl or C6-C14, the H on the aryl of the C6-C14 is unsubstituted Or replace by the substituent B of 1-4, the substituent B be the alkyl of C1-C4, the alkoxy of C1-C4, C1-C4 fluoroalkyl, Fluoroalkyloxy, F or the Cl of C1-C4；
Or R12With R13It connect cyclization with two carbon on five-membered ring, forms C9-C15Benzo naphthenic base.
The aryl is generally phenyl, naphthalene, and the * in formula (1) represents asymmetric carbon atom.
As a further improvement, the R1-R10The respectively ring of independent preferably hydrogen, the alkyl of C1-C6, C3~C8 The aryl of alkyl, the alkoxy of C1~C4 or C6-C10；
R11With R12The respectively preferably aryl of hydrogen, the alkyl of C1-C6 or C6-C14；
R13The preferably aryl of the alkyl of C1-C6, benzyl or C6-C10.
R14The preferably aryl of hydrogen, the alkyl of C1-C6, benzyl or C6-C10.
Further, R1The preferably aryl of hydrogen, the alkyl of C1-C6, the naphthenic base of C3~C8 or C6-C10, is more preferably selected The naphthenic base of hydrogen, the alkyl of C1-C6, C3~C6 is selected, hydrogen, methyl, ethyl, isopropyl, methoxyl group or cyclohexyl are more preferably selected.
R2, R3, R4, R5, R6, R7, R8, R9, R10The preferably alkyl or phenyl of hydrogen, the alkoxy of C1-C4, C1-C6, more Preferential selection hydrogen, methyl, ethyl, propyl, isopropyl, normal-butyl, methoxyl group or phenyl.
R11, R12More preferably select H, methyl, ethyl, isopropyl or phenyl, more preferable R11, R12It is all H.
R13More preferably methyl, isopropyl, tertiary butyl, phenyl, indenyl or benzyl；
Or preferably R12With R13It connect cyclization with two carbon on five-membered ring, forms indane.
R14More preferably phenyl or substituted-phenyl, the substituted-phenyl are the phenyl for having on phenyl ring 1~3 substituent B, institute It is preferably the alkyl of C1-C4, the alkoxy of C1-C4, trifluoromethyl, more preferably methyl, ethyl, isopropyl, uncle to state substituent B Butyl, methoxyl group or trifluoromethyl.
The most preferably described quinoline amine compounds are one of following：
Second aspect, the present invention also provides a kind of preparation method of the quinoline amine compounds, the method is：
Under inert gas environment, in the presence of transition-metal catalyst and ligand, alkali, in organic solvent A, with formula (2) Shown in halides shown in aminoquinoline and formula (3) be raw material or with shown in quinoline halides shown in formula (4) and formula (5) Aniline be raw material carry out coupling reaction, be made formula (1) shown in quinoline aminated compounds；The transition-metal catalyst is palladium (Pd) complex compound, preferably zero-valence palladium complex, more preferably Pd2(dba)3, Pd (dba)2；The ligand is organic phosphatization Conjunction object, preferably 1,1'Bis- (diphenylphosphine) ferrocene (dppf), (±) -2,2'Double-(diphenyl phosphine) -1,1'Dinaphthalene (BINAP) or the bis- diphenylphosphine -9,9- xanthphos (Xantphos) of 4,5-；The alkali is the alkali metal salt of alcohol, excellent Select the sylvite or sodium salt of alcohol, more preferably sodium tert-butoxide and potassium tert-butoxide；
X is O, S or NR in formula (3)14；Y is F, Cl, Br or I, preferably Br or I；
X is O, S or NR in formula (5)14；Y is F, Cl, Br or I, preferably Br or I in formula (4)；
R in formula (2)1, R2, R3, R4, R5, R6, R7, R8, R9And R10Respectively stand alone as hydrogen, halogen, the alkyl of C1-C10, C1- The aryl of the fluoroalkyl of C4, the alkoxy of C1-C4, the naphthenic base of C3~C10 or C6-C14；
R11With R12Respectively stand alone as the aryl of hydrogen, the alkyl of C1-C10 or C6-C14；
R13For the alkyl of C1-C12, the aryl of the naphthenic base of C3~C12, benzyl or C6-C14, the wherein alkyl of C1-C12 On H it is not substituted or replaced by the alkoxy of 1-2 C1-C4；H in the naphthenic base of the C3~C12 it is not substituted or by The alkoxy of 1-3 C1-C4 alkyl or C1-C4 replace, and the H on the aryl of the C6-C14 is unsubstituted or is replaced by 1-3 Base A substitution, the substituent A be the alkyl of C1-C4, the alkoxy of C1-C4, the fluoroalkyl of C1-C4, C1-C4 Fluoroalkyloxy, F or Cl；
R14For hydrogen, the aryl of the alkyl of C1-C10, benzyl or C6-C14, the H on the aryl of the C6-C14 is unsubstituted Or replace by the substituent B of 1-4, the substituent B be the alkyl of C1-C4, the alkoxy of C1-C4, C1-C4 fluoroalkyl, Fluoroalkyloxy, F or the Cl of C1-C4；
Or R12With R13It connect cyclization with two carbon on five-membered ring, forms C9-C15Benzo naphthenic base；
R in formula (3), formula (4) and formula (5)1-R14Same formula (2).* in formula (3) and formula (5) represents asymmetric carbon atom.
That is, the preparation method of quinoline amine compounds of the present invention is one of the following：1) under inert gas environment, In the presence of transition-metal catalyst and ligand, alkali, in organic solvent, shown in aminoquinoline shown in formula (2) and formula (3) Halides are that raw material carries out coupling reaction, and quinoline aminated compounds shown in formula (1) is made；Or 2) under inert gas environment, In the presence of transition-metal catalyst and ligand, alkali, in organic solvent, shown in quinoline halides shown in formula (4) and formula (5) Aniline compound be raw material carry out coupling reaction, be made formula (1) shown in quinoline aminated compounds.
As a further improvement, the reaction temperature of coupling reaction is 50 DEG C to 200 DEG C, the reaction time is 1 hour to 72 Hour.
As a further improvement, the organic solvent A of coupling reaction be benzene, dimethylformamide, carbon tetrachloride, toluene, Any one in petroleum ether, dioxane, tetrahydrofuran, ether, chloroform, dimethylbenzene, acetonitrile, preferably toluene or two Toluene.
The inert gas environment, usually in a nitrogen environment.
As a further improvement, aminoquinoline shown in halides, formula (2) shown in formula (3), transition metal-catalyzed Agent, ligand, alkali the ratio between the amount of substance be 1:0.1-4:0.01-0.5:0.01-0.5：1~4, preferably 1:1~2:0.02~ 0.3:0.1~0.3:1~3.
As a further improvement, aniline shown in quinoline bromo-derivative, formula (5) shown in formula (4), transition metal-catalyzed Agent, ligand, alkali the ratio between the amount of substance be 1:0.1-4:0.01-0.5:0.01-0.5：1~4, preferably 1:1~2:0.02~ 0.3:0.1~0.3:1~3.
The organic solvent A volumetric usage is with quinoline bromo-derivative substance shown in halides shown in formula (3) or formula (4) Amount is calculated as 0.5~8ml/mmol, preferably 2-8ml/mmol.
After coupling reaction of the present invention, stops heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate Washing, filtrate concentration, column chromatography for separation obtain product.
The present invention also provides application of the quinoline amine compounds shown in formula (1) in preparing chiral organic boron ester compounds, The application process is：In organic solvent B, transistion metal compound MYnExist with quinoline amine compounds shown in formula (1) Under, with pinacol borine shown in aromatic olefin compound shown in formula (7) and formula (8) (HBPin, chemistry complete entitled 4,4,5, 5- tetramethyls -1,3, penta ring of 2- dioxies boron) it is that raw material carries out asymmetric geneva hydroboration, it is prepared shown in formula (6) Chiral organic boron ester compounds；
In formula (7), Ar is phenyl or substituted-phenyl, and the substituent group of the substituted-phenyl is the alkyl of C1-C6, C1-C6 Alkoxy, methyl mercapto, CF3, F, Cl or Br, preferably methyl, tertiary butyl, F or Cl；The same formulas of Ar (7) in formula (6)；
The transistion metal compound MYnMiddle M is transition-metal Fe or Co；Y is F, Cl, Br, I, OSO2CH3、OSO2CF3、 O(CH3) C=CHCOCH3、OCOCH2CH3、OCOCH3、ClO4In any one；N is the number of Y, is 2 or 3, the preferably described mistake Cross metallic compound MYnFor frerrous chloride or cobalt acetate；
The organic solvent B is toluene, ether or Isosorbide-5-Nitrae-dioxane.
Further, as transistion metal compound MYnFor frerrous chloride when, NaBHEt is added in the reaction3, i.e., organic molten Agent B, NaBHEt3, in the presence of quinoline amine compounds shown in frerrous chloride and formula (1), with aromatic olefin chemical combination shown in formula (7) Pinacol borine shown in object and formula (8) is that raw material carries out asymmetric geneva hydroboration, and hand shown in formula (6) is prepared Property organic boron ester compounds；Pinacol borine shown in aromatic olefin compound shown in the formula (7) and formula (8), NaBHEt3, transistion metal compound MYnIt is 1 with the ratio between amount of quinolinamine combinations of materials shown in formula (1)：0.2~2.0： 0.01~0.2：0.005~0.1：0.005~0.12, preferably 1:1-2:0.1-0.2:0.02-0.05:0.03-0.06；
As transistion metal compound MYnFor cobalt acetate when, the quinoline amination shown in organic solvent B, cobalt acetate and formula (1) In the presence of closing object, carried out using pinacol borine shown in aromatic olefin compound shown in formula (7) and formula (8) as raw material asymmetric Chiral organic boron ester compounds shown in formula (6) are prepared in geneva hydroboration；Aromatic olefin shown in the formula (7) Compound and pinacol borine, transistion metal compound MY shown in formula (8)nWith quinolinamine combinations of materials shown in formula (1) The ratio between amount be 1：0.2~2.0：0.005~0.1：0.005~0.12, preferably 1:1-2:0.02-0.05:0.03-0.06；.
The organic solvent B volumetric usage is calculated as 0.25~5 ml/ with the amount of aromatic olefin substance shown in formula (7) Mmol, preferably 1-2ml/mmol.
Further, the asymmetric geneva hydroboration condition is 0~50 DEG C of 1~72h of reaction.
After asymmetry geneva hydroboration of the present invention, reaction solution silica gel filtering, ethyl acetate washs, and filtrate is dense Contracting, column chromatography for separation obtain product.
Transition metal salt MY of the present inventionnCarbon carbon with compound (1) through complexes ira situ for prochiral organic compounds is double Asymmetric reduction addition is carried out on key, to prepare chiral organic boron ester compounds.
The organic solvent A and organic solvent B are organic solvent, and letter itself does not have meaning.
The beneficial effects are mainly as follows：
The present invention provides a kind of novel chiral oxazolines or imidazoline phenylchinoline amine compounds, and provide one The easy method for synthesizing such compound.
The present invention provides chiral oxazoline of the invention or imidazoline phenylchinoline amine compounds and transition metal M Y 'nIt is former Purposes of the position complex compound as homogeneous catalyst, catalyst in the carbon carbon atom double bond of prochiral organic compounds by carrying out The addition of asymmetric reduction is used to prepare chiral organoboron compound, and preferred prochirality is acted on not for asymmetric reduction Saturated compounds is styrene compound.
Can chiral organic boron ester compounds prepared in accordance with the present invention be a kind of important organic synthesis intermediate, especially Pharmaceutical preparation, fragrance and fumet, agricultural chemicals production in terms of.
Specific implementation mode
Technical scheme of the present invention is described further with specific embodiment below, but protection scope of the present invention is not It is limited to this.
Following embodiment is for explaining the present invention.All reactions carry out in nitrogen and the solvent of degassing.
In the embodiment of the present invention, formula (2) be it is commercially available, halide formula (3) according to document (Org.Lett. 2008, 10,917；Tetrahedron:Asymmetry, 2016,27,163.) it prepares.
Room temperature described in the embodiment of the present invention refers to 25-30 DEG C.
Embodiment 1：The preparation of compound (1-1)
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0700g, 0.075 Mmol), double Diphenyl phosphino ferrocenes (dppf) (0.0745g, 0.13mmol) and toluene (10mL), are stirred at room temperature 10 minutes, after The addition 8- aminoquinolines (2-1) (0.2166g, 1.5mmol) into bottle successively, (S)-2- (2- bromophenyls) isopropyl-4-4-, - oxazoline of 5- dihydros (3-1) (0.4100g, 1.5mmol) and NaOtBu (0.2780g, 2.9mmol) is replaced 3 times with nitrogen, 110 DEG C of back flow reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, cleaning solution concentration It is flowed out to no liquid, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains shallow Yellow solid product (1-1) (0.3178g, 64% yield).
1H NMR(400MHz,CDCl3):δ 11.82 (s, 1H), 8.93-8.74 (m, 1H), 8.11 (dd, J=8.4,1.6 Hz, 1H), 7.95-7.71 (m, 3H), 7.53-7.27 (m, 4H), 6.87 (dd, J=8.0,6.8Hz, 1H), 4.42 (dd, J= 9.2,8.0Hz, 1H), 4.18 (dd, J=16.8,8.8Hz, 1H), 4.02 (t, J=8.4Hz, 1H), 1.90-1.69 (m, 1H), 1.19 (d, J=6.4Hz, 3H), 1.02 (d, J=6.8Hz, 3H)；13C NMR:(75.5 MHz,CDCl3):δ163.0,148.1, 143.5,140.6,139.1,135.8,131.5,130.1,129.1,126.7, 121.4,118.6,118.3,115.1, 113.3,111.7,73.5,69.5,33.7,19.3,18.9；HRMS(EI) calculated for[C21H21N3O]+ requires m/z 331.1685,found m/z 331.1687.
Embodiment 2
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.2260g,0.25 Mmol), dppf (0.2845g, 0.51mmol) and toluene (10mL), are stirred at room temperature 10 minutes, after successively into bottle be added 8- ammonia Base quinoline (2-1) (0.7228g, 5.0mmol),-oxazoline (3-2) of (S) -2- (2- bromophenyls) -4- tertiary butyls -4,5- dihydro (1.4208g, 5.0mmol) and KOtBu (1.1200g, 10.1mmol) is replaced 3 times, 60 DEG C of reaction 48h with nitrogen.Stop adding Heat is restored after reaction solution to room temperature, and silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid outflow, silica gel column chromatography (eluant, eluent is petroleum ether：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains faint yellow oil product 1-2 (0.5760g, 33% yield).
1H NMR(400MHz,CDCl3):δ 11.83 (s, 1H), 8.82 (dd, J=4.0,1.6Hz, 1H), 8.11 (dd, J =8.4,1.6Hz, 1H), 7.93-7.75 (m, 3H), 7.47-7.30 (m, 4H), 6.92-6.81 (m, 1H), 4.32 (dd, J= 9.6,7.6Hz, 1H), 4.24 (dd, J=9.6,8.0Hz, 1H), 4.15 (dd, J=8.0,7.6Hz, 1H), 1.03 (s, 9H)；13C NMR(101MHz,CDCl3):δ162.8,148.0,143.5,140.5,139.0,135.8, 131.5,130.1,129.1, 126.7,121.4,118.5,118.3,115.1,113.3,111.5,76.6,67.0,33.9, 25.8；HRMS(EI) calculated for[C22H23N3O]+requires m/z 345.1841,found m/z 345.1844.
Embodiment 3
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.1308g,0.14 Mmol), dppf (0.2845g, 0.31mmol) and toluene (6.0mL), are stirred at room temperature 10 minutes, after successively into bottle be added 8- ammonia Base quinoline (2-1) (0.4401g, 3.05mmol),-oxazoline (3-3) of (S) -2- (2- bromophenyls) -4- benzyls -4,5- dihydro (0.9528g, 3.0mmol) and NaOtBu (0.5706g, 5.94mmol) is replaced 3 times, 110 DEG C of back flow reaction 12h with nitrogen.Stop It only heats, restores to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid outflow, silicagel column (eluant, eluent is petroleum ether to chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains faint yellow oil product 1-3 (0.4420g, 38% yield).
1H NMR(400MHz,CDCl3):δ 11.59 (s, 1H), 8.79 (dd, J=4.0,1.6Hz, 1H), 8.04 (dd, J =8.4,1.6Hz, 1H), 7.85 (dd, J=8.0,1.6Hz, 1H), 7.78 (d, J=8.0Hz, 2H), 7.43-7.20 (m, 6H), 7.14-7.02 (m, 3H), 6.87-6.79 (m, 1H), 4.80-4.63 (m, 1H), 4.29 (dd, J=9.2,8.4Hz, 1H), 4.00 (t, J=8.0Hz, 1H), 3.20 (dd, J=13.6,6.0Hz, 1H), 2.81 (dd, J=13.6,7.6Hz, 1H) ；13C NMR(101MHz,CDCl3):δ163.5,148.3,143.7,140.7, 139.1,138.1,135.8,131.6, 130.2,129.2,129.1,128.2,126.6,126.2,121.4,118.9, 118.3,115.2,113.2,112.3, 70.2,68.0,41.8；HRMS(EI)calculated for[C25H21N3O]+ requires m/z 379.1685,found m/z 379.1685.
Embodiment 4
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0972g,0.11 Mmol), dppf (0.1128g, 0.20mmol) and toluene (5.0mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.3208g, 2.0mmol),-oxazole of (S) -2- (2- bromophenyls) -4- isopropyls -4,5- dihydro Quinoline (3-1) (0.5462g, 2.0mmol) and NaOtBu (0.3906g, 4.0 mmol) is replaced 3 times with nitrogen, and 110 DEG C of reflux are anti- Answer 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid stream Go out, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains light yellow solid production Object 1-4 (0.5286 g, 75% yield).
1H NMR(400MHz,CDCl3):δ 11.47 (s, 1H), 7.99 (d, J=8.4Hz, 1H), 7.90-7.76 (m, 3H), 7.39-7.26 (m, 4H), 6.85 (dd, J=8.0,7.2Hz, 1H), 4.39 (dd, J=9.6,8.0Hz, 1H), 4.20 (dd, J=16.4,8.0Hz, 1H), 4.04 (t, J=8.0Hz, 1H), 2.75 (s, 3H), 1.89-1.77 (m, 1H), 1.11 (d, J=6.8Hz, 3H), 0.99 (d, J=6.8Hz, 3H)；13C NMR(101MHz,CDCl3): δ162.9,157.0,143.7, 140.1,138.6,136.1,131.4,130.1,127.3,125.6,122.3,118.7, 118.3,115.6,113.5, 112.3,73.4,69.1,33.5,25.4,19.2,19.0；HRMS(EI)calculated for[C22H23N3O]+requires m/z 345.1841,found m/z 345.1841.
Embodiment 5
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0656g,0.072 Mmol), dppf (0.0896g, 0.16mmol) and toluene (7.5mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.2408g, 1.5mmol),-oxazole of (S) -2- (2- bromophenyls) -4- tertiary butyls -4,5- dihydro Quinoline (3-2) (0.4218g, 1.5mmol) and NaOtBu (0.2779g, 2.9 mmol) is replaced 3 times with nitrogen, and 110 DEG C of reflux are anti- Answer 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid stream Go out, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains light yellow solid production Object 1-5 (0.4050 g, 74% yield).
1H NMR(400MHz,CDCl3):δ 11.38 (s, 1H), 7.99 (d, J=8.4Hz, 1H), 7.89-7.84 (m, 1H), 7.83-7.75 (m, 2H), 7.39-7.26 (m, 4H), 6.88-6.82 (m, 1H), 4.30 (dd, J=8.8,7.2 Hz, 1H),4.24-4.12(m,2H),2.74(s,3H),0.99(s,9H)；13C NMR(101MHz,CDCl3): δ162.9,157.1, 143.9,140.2,138.6,136.1,131.4,130.1,127.4,125.6,122.4,118.8, 118.3,115.7, 113.5,112.6,76.8,67.0,34.0,26.0,25.5；HRMS(ESI)calculated for [M+Na]+ [C23H25N3ONa]+requires m/z 382.1895,found m/z 382.1891.
Embodiment 6
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0648g,0.071 Mmol), dppf (0.0845g, 0.15mmol) and toluene (7.5mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.2408g, 1.5mmol),-oxazoline of (S) -2- (2- bromophenyls) -4- benzyls -4,5- dihydro (3-3) (0.4628g, 1.5mmol) and NaOtBu (0.2602g, 2.7mmol) is replaced 3 times, 110 DEG C of back flow reactions with nitrogen 48h.Stopping heating, restores to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid outflow, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains product as light yellow solid 1-6 (0.4024g, 70% yield).
1H NMR(400MHz,CDCl3):δ 11.69 (s, 1H), 8.02 (d, J=8.4Hz, 1H), 7.90-7.84 (m, 2H), 7.82-7.77 (m, 1H), 7.42-7.34 (m, 2H), 7.30 (d, J=8.4Hz, 2H), 7.27-7.24 (m, 2H), 7.21-7.10 (m, 3H), 6.91-6.77 (m, 1H), 4.81-4.69 (m, 1H), 4.31 (dd, J=8.8,8.8 Hz, 1H), 4.09 (dd, J=8.0,7.6Hz, 1H), 3.34 (dd, J=13.6,5.2Hz, 1H), 2.86 (dd, J=13.6,8.4Hz, 1H),2.73(s,3H)；13C NMR(101MHz,CDCl3):δ163.6,156.8,143.8, 140.0,138.5,138.1, 136.1,131.7,130.2,129.3,128.4,127.3,126.4,125.7,122.2, 118.5,118.2,115.3, 113.2,111.9,70.2,68.3,42.0,25.5；HRMS(ESI)calculated for [M+Na]+[C26H23N3ONa]+ requires m/z 416.1739,found m/z 416.1752.
Embodiment 7
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0503g,0.055 Mmol), dppf (0.0589g, 0.11mmol) and toluene (5.0mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.1589g, 1.0mmol),-oxazoline of (S) -2- (2- bromophenyls) -4- indenyls -4,5- dihydro (3-4) (0.3289g, 1.05mmol) and NaOtBu (0.1950g, 2.03 mmol) is replaced 3 times with nitrogen, and 110 DEG C of reflux are anti- Answer 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid stream Go out, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains light yellow solid production Object 1-7 (0.3320 g, 84% yield).
1H NMR(400MHz,CDCl3):δ 11.48 (s, 1H), 8.01 (d, J=8.4Hz, 1H), 7.87 (dd, J=7.6, 1.6Hz,1H),7.81-7.70(m,2H),7.61-7.54(m,1H),7.37-7.26(m,4H),7.24-7.17 (m,3H), 6.86-6.75 (m, 1H), 5.88 (d, J=8.0Hz, 1H), 5.48-5.32 (m, 1H), 3.51 (dd, J=18.0,6.8Hz, 1H), 3.39 (d, J=17.2Hz, 1H), 2.89 (s, 3H)；13C NMR(101MHz, CDCl3):δ163.6,156.7,143.7, 142.3,140.0,139.7,138.6,136.1,131.6,130.3,128.3, 127.3,125.7,125.2,122.2, 118.5,118.3,115.6,113.5,111.9,81.5,77.3,39.7,25.7； HRMS(ESI)calculated for[M+ Na]+[C26H21N3ONa]+requires m/z 414.1582,found m/z 414.1592.
Embodiment 8
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0691g,0.075 Mmol), dppf (0.0853g, 0.15mmol) and dimethylbenzene (7.5mL), are stirred at room temperature 10 minutes, after 2- is added into bottle successively Cyclohexyl -8- aminoquinolines (2-3) (0.3390g, 1.5mmol), (S) -2- (2- bromophenyls) -4- isopropyls -4,5- dihydro - Oxazoline (3-1) (0.4024g, 1.5mmol) and NaOtBu (0.3021g, 3.1 mmol) is replaced 3 times with nitrogen, and 200 DEG C anti- Answer 1h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid stream Go out, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains pale yellowish oil production Object 1-8 (0.4466g, 72% yield).
1H NMR(400MHz,CDCl3):δ 11.31 (s, 1H), 7.98 (d, J=8.8Hz, 1H), 7.88 (dd, J=8.0, 1.2Hz, 1H), 7.82 (d, J=8.4Hz, 1H), 7.75 (d, J=7.6Hz, 1H), 7.37-7.23 (m, 4H), 6.87-6.80 (m, 1H), 4.36-4.29 (m, 1H), 4.27-4.19 (m, 1H), 4.07 (s, J=7.6Hz, 1H), 3.00-2.90 (m, 1H), 2.09-2.00 (m, 2H), 1.91-1.58 (m, 6H), 1.50-1.38 (m, 2H), 1.37-1.28 (m, 1H), 1.02 (d, J= 7.2Hz, 3H), 0.91 (d, J=6.8Hz, 3H)；13C NMR(101 MHz,CDCl3):164.6,162.8,143.8,139.8, 138.8,136.1,131.3,130.2,127.7,125.5, 119.9,118.6,118.2,115.6,113.6,112.4, 73.1,68.2,47.2,32.8,32.7,26.6,26.1,19.3, 18.0；HRMS(EI)calculated for[C27H31N3O ]+requires m/z 377.1528,found m/z 377.1528.
Embodiment 9
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0920g,0.10 Mmol), dppf (0.1120g, 0.20mmol) and toluene (10.0mL), are stirred at room temperature 10 minutes, after 2- is added into bottle successively Isopropyl -5,6- dimethyl -8- aminoquinolines (2-4) (0.3448g, 2.0mmol), (S) -2- (2- bromophenyls) -4- isopropyls - oxazoline (3-1) (0.5318g, 2.0mmol) of base -4,5- dihydros and NaOtBu (0.3848g, 4.0mmol), is replaced with nitrogen 3 times, 110 DEG C of back flow reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, cleaning solution It is concentrated into no liquid outflow, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.7) obtains To pale yellowish oil product 1-9 (0.5328g, 66% yield).
1H NMR(400MHz,CDCl3):δ 11.20 (s, 1H), 8.24 (d, J=8.8Hz, 1H), 7.86 (dd, J=8.0, 1.6Hz, 1H), 7.78 (d, J=8.4Hz, 1H), 7.63 (s, 1H), 7.39-7.29 (m, 2H), 6.81 (dd, J=8.0, 7.2Hz, 1H), 4.39-4.29 (m, 1H), 4.27-4.17 (m, 1H), 4.07 (dd, J=8.0,7.6Hz, 1H), 3.36-3.21 (m, 1H), 2.49 (s, 3H), 2.43 (s, 3H), 1.93-1.79 (m, 1H), 1.40 (d, J=3.2 Hz, 3H), 1.38 (d, J= 3.2Hz, 3H), 1.01 (d, J=6.8Hz, 3H), 0.91 (d, J=6.8Hz, 3H)；13C NMR(101MHz,CDCl3): 163.9,162.8,144.3,139.0,136.3,132.6,132.4, 131.4,130.2,126.9,122.4,119.1, 117.6,116.2,115.3,113.1,73.1,68.5,36.8,33.0, 22.6,22.6,20.9,19.3,18.3,13.7； HRMS(EI)calculated for[C26H31N3O]+requires m/z 401.2467,found m/z 401.2471.
Embodiment 10
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0885g,0.097 Mmol), dppf (0.1128g, 0.20mmol) and toluene (10.0mL), are stirred at room temperature 10 minutes, after 6- is added into bottle successively Methoxyl group -8- aminoquinolines (2-5) (0.3549g, 2.0mmol), (S) -2- (2- bromophenyls) -4- isopropyls -4,5- dihydro - Oxazoline (3-1) (0.5466g, 2.0mmol) and NaOtBu (0.3866g, 4.0 mmol) is replaced 3 times with nitrogen, and 110 DEG C are returned Stream reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into aneroid Body flows out, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) separation (Rf=0.6) obtains light yellow solid Body product 1-10 (0.4870 g, 64% yield).
1H NMR(400MHz,CDCl3):δ 11.83 (s, 1H), 8.71-8.65 (m, 1H), 7.99 (dd, J=8.1,1.5 Hz, 1H), 7.92-7.85 (m, 2H), 7.47 (d, J=2.4Hz, 1H), 7.42-7.33 (m, 2H), 6.93-6.85 (m, 1H), 6.62 (d, J=2.4Hz, 1H), 4.46-4.38 (m, 1H), 4.23-4.13 (m, 1H), 4.02 (dd, J=8.4,8.1Hz, 1H), 3.91 (s, 3H), 1.86-1.72 (m, 1H), 1.19 (d, J=6.6Hz, 3H), 1.02 (d, J=6.6 Hz, 3H)；13C NMR(101MHz,CDCl3):δ162.9,158.3,145.6,143.1,140.2,137.4, 134.6,131.6,130.1, 129.9,121.9,118.7,115.7,113.7,103.5,96.4,77.3,77.0,76.7, 73.5,69.6,55.3,33.7, 19.3,18.9；HRMS(EI)calculated for[C22H23N3O2]+requires m/z 361.1790,found m/z 361.1790.
Embodiment 11
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0432g,0.047 ), mmol the bis- diphenylphosphine -9,9- xanthphos (Xantphos) (0.0568g, 0.098mmol) of 4,5- and toluene (3.0mL) is stirred at room temperature 10 minutes, after successively into bottle be added the bromo- 4- methoxyl groups -2- methylquinolines (4-1) of 8- (0.1171g, 0.46mmol), (S) -2- (4- isopropyl -4,5- dihydro-oxazole quinolines base) -2- aniline (5-1) (0.1018g, 0.50mmol) and NaOtBu (0.0954g, 1.0mmol) is replaced 3 times, 110 DEG C of back flow reaction 48h with nitrogen.Stop heating, waits for Reaction solution restores to room temperature, and silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid outflow, silica gel column chromatography (elution Agent is petroleum ether：Ethyl acetate=20:1, v/v) separation (Rf=0.6) obtain product as light yellow solid 1-11 (0.1350g, 77% yield).1H NMR(400 MHz,CDCl3):δ11.41(s,1H),7.85(dd,1H),7.83-7.73(m,2H),7.63 (dd, J=8.4,0.8 Hz, 1H), 7.36-7.28 (m, 2H), 6.86-6.79 (m, 1H), 6.64 (s, 1H), 4.38 (dd, J= 9.2,8.0Hz, 1H), 4.22-4.14 (m, 1H), 4.02 (dd, J=8.4,8.0Hz, 1H), 3.99 (s, 3H), 2.70 (s, 3H), 1.86-1.77 (m, 1H), 1.10 (d, J=6.6Hz, 3H), 0.98 (d, J=6.6Hz, 3H)；13C NMR(101 MHz, CDCl3):δ162.9,162.3,157.9,143.8,141.0,138.3,131.3,130.0,124.6,120.5, 118.1, 115.5,113.4,112.9,112.7,100.9,73.4,69.1,55.4,33.4,26.0,19.2,19.0； HRMS(ESI) calculated for[M+Na]+[C23H25N3O2Na]+requires m/z 384.1688,found m/z 384.1700.
Embodiment 12
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0450g,0.049 Mmol), dinaphthalene hexichol phosphorus, 1,1'Dinaphthalene -2,2'Double diphenyl phosphines (BINAP) (0.0618g, 0.099mmol) and toluene (3.0mL) is stirred at room temperature 10 minutes, after successively into bottle be added the bromo- 4- methoxyl groups -2- methylquinolines (4-1) of 8- (0.1004g, 0.40mmol), (S) -2- (4- isopropyl -4,5- dihydro-oxazole quinolines base) -2- aniline (5-1) (0.0908g, 0.44mmol) and NaOtBu (0.0956g, 1.0mmol) is replaced 3 times, 110 DEG C of back flow reaction 48h with nitrogen.Stop heating, waits for Reaction solution restores to room temperature, and silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into no liquid outflow, silica gel column chromatography (elution Agent is petroleum ether：Ethyl acetate=20:1, v/v) separation (Rf=0.6) obtain product as light yellow solid 1-11 (0.1393g, 93% yield).1H NMR(400 MHz,CDCl3):δ11.41(s,1H),7.85(dd,1H),7.83-7.73(m,2H),7.63 (dd, J=8.4,0.8 Hz, 1H), 7.36-7.28 (m, 2H), 6.86-6.79 (m, 1H), 6.64 (s, 1H), 4.38 (dd, J= 9.2,8.0Hz, 1H), 4.22-4.14 (m, 1H), 4.02 (dd, J=8.4,8.0Hz, 1H), 3.99 (s, 3H), 2.70 (s, 3H), 1.86-1.77 (m, 1H), 1.10 (d, J=6.6Hz, 3H), 0.98 (d, J=6.6Hz, 3H)；13C NMR(101 MHz, CDCl3):δ162.9,162.3,157.9,143.8,141.0,138.3,131.3,130.0,124.6,120.5, 118.1, 115.5,113.4,112.9,112.7,100.9,73.4,69.1,55.4,33.4,26.0,19.2,19.0； HRMS(ESI) calculated for[M+Na]+[C23H25N3O2Na]+requires m/z 384.1688,found m/z 384.1700.
Embodiment 13
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0445g,0.049 Mmol), dppf (0.0547g, 0.10mmol) and toluene (5.0mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.1607g, 1.0mmol), (S)-(1- phenyl -2- (2- iodobenzenes) base -4- tertiary butyls -4,5- bis- Hydrogen) -1H- imidazoles (3-5) (0.4051g, 1.0mmol) and NaOtBu (0.1940 g, 2.0mmol), with nitrogen replace 3 times, 110 DEG C back flow reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, and cleaning solution is concentrated into No liquid flows out, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=5:1, v/v) separation (Rf=0.4) obtains pale yellow Color solid product 1-12 (0.3066g, 70% yield).
1H NMR(400MHz,CDCl3):δ 9.93 (s, 1H), 7.97 (d, J=8.4Hz, 1H), 7.73 (d, J=8.0 Hz, 1H), 7.50 (d, J=8.0Hz, 1H), 7.31-7.18 (m, 5H), 7.09 (dd, J=8.0,7.6Hz, 2H), 6.91 (dd, J= 7.6,7.2Hz, 1H), 6.85-6.71 (m, 3H), 4.11 (dd, J=10.8,8.4Hz, 1H), 4.01 (dd, J=10.8, 7.2Hz, 1H), 3.62 (dd, J=9.2,8.0Hz, 1H), 2.74 (s, 3H), 1.00 (s, 9H)；13C NMR(101MHz, CDCl3):δ160.0,156.5,143.4,141.7,139.5,139.1,136.0, 130.7,129.8,128.5,127.1, 125.7,123.0,122.3,122.2,121.2,120.3,119.1,117.2, 109.8,74.6,54.0,34.0,26.1, 25.3；HRMS(EI)calculated for[C29H30N4]+requires m/z 434.2470,found m/z 434.2470.
Embodiment 14
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0446g,0.049 Mmol), dppf (0.0566g, 0.10mmol) and toluene (5.0mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.1596g, 1.0mmol), (S)-(1- phenyl -2- (2- iodobenzenes) base -4- isopropyls -4,5- two Hydrogen) -1H- imidazoles (3-6) (0.3378g, 0.86mmol) and NaOtBu (0.1926g, 2.0mmol) is replaced 3 times with nitrogen, 110 DEG C of back flow reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, cleaning solution concentration It is flowed out to no liquid, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=5:1, v/v) separation (Rf=0.4) obtains shallow Yellow solid product 1-13 (0.2715g, 75% yield).
1H NMR(400MHz,CDCl3):10.06 (s, 1H), 7.97 (d, J=8.8Hz, 1H), 7.74 (d, J=8.4 Hz, 1H), 7.50 (d, J=7.6Hz, 1H), 7.30-7.25 (m, 3H), 7.18 (d, J=8.4Hz, 1H), 7.07 (dd, J=8.0, 7.6Hz, 2H), 6.89 (dd, J=7.6,7.2Hz, 1H), 6.84-6.71 (m, 3H), 4.24-4.12 (m, 1H), 4.03 (dd, J =10.4,9.2Hz, 1H), 3.60 (dd, J=8.8,8.4Hz, 1H), 2.75 (s, 3H), 2.02-1.93 (m, 1H), 1.09 (d, J=6.8Hz, 3H), 0.96 (d, J=6.8Hz, 3H)；13C NMR(101 MHz,CDCl3):δ159.7,156.2,142.9, 141.4,139.2,138.8,135.9,130.6,129.8,128.4, 126.9,125.7,122.8,122.1,121.8, 120.9,120.1,118.8,116.9,109.0,70.7,55.2,33.1, 25.1,19.0,18.2；HRMS(EI) calculated for[C28H28N4]+requires m/z 420.2314,found m/z 420.2314.
Embodiment 15
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0450g,0.049 Mmol), dppf ((0.0553g, 0.10mmol) and toluene (5.0mL), is stirred at room temperature 10 minutes, after 2- is added into bottle successively Methyl-8-aminoquinoline (2-2) (0.1598g, 1.0mmol), (S)-(1- phenyl -2- (2- iodobenzenes) base -4- phenyl -4,5- two Hydrogen) -1H- imidazoles (3-7) (0.4179g, 0.98mmol) and NaOtBu (0.1937g, 2.0 mmol) is replaced 3 times with nitrogen, 110 DEG C of back flow reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, cleaning solution concentration It is flowed out to no liquid, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=5:1, v/v) separation (Rf=0.4) obtains shallow Yellow solid product 1-14 (0.2171 g, 48% yield).
1H NMR(400MHz,CDCl3):10.40 (s, 1H), 7.95 (d, J=8.0Hz, 1H), 7.78 (d, J=8.4 Hz, 1H),7.52-7.44(m,3H),7.36-7.28(m,3H),7.23-7.15(m,3H),7.11-7.04(m,2H), 6.94- 6.87 (m, 1H), 6.87-6.73 (m, 3H), 5.51 (dd, J=10.4,9.6Hz, 1H), 4.42 (dd, J=10.4,9.6Hz, 1H), 3.80 (dd, J=9.2,9.2Hz, 1H), 2.42 (s, 3H)；13C NMR(101MHz, CDCl3):δ161.1,156.3, 143.7,142.7,141.5,139.1,138.6,135.8,130.7,130.2,128.5, 128.3,126.9,126.8, 126.8,125.7,123.3,122.1,120.6,120.1,118.7,116.8,108.4, 68.0,60.6,24.8；HRMS (EI)calculated for[C31H26N4]+requires m/z 454.2157,found m/z 454.2154.
Embodiment 16
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0470g,0.051 Mmol), dppf (0.0556g, 0.10mmol) and toluene (5.0mL), are stirred at room temperature 10 minutes, after successively into bottle be added 2- first Base -8- aminoquinolines (2-2) (0.1594g, 1.0mmol), (S)-(1- phenyl -2- (2- iodobenzenes) base -4- benzyls -4,5- bis- Hydrogen) -1H- imidazoles (3-8) (0.4277g, 0.98mmol) and NaOtBu (0.1920g, 2.0 mmol) is replaced 3 times with nitrogen, 110 DEG C of back flow reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, ethyl acetate is washed, cleaning solution concentration It is flowed out to no liquid, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=5:1, v/v) separation (Rf=0.4) obtains shallow Yellow solid product 1-15 (0.1926 g, 42% yield).
1H NMR(400MHz,CDCl3):δ 10.33 (s, 1H), 7.94 (d, J=8.8Hz, 1H), 7.76 (d, J=8.4 Hz, 1H), 7.52 (d, J=7.6Hz, 1H), 7.33-7.10 (m, 10H), 7.04-6.95 (m, 2H), 6.84 (dd, J=7.6, 7.2Hz, 1H), 6.77 (dd, J=7.6,7.2Hz, 1H), 6.62 (d, J=7.6Hz, 2H), 4.80-4.51 (m, 1H), 3.95 (dd, J=9.6,9.6Hz, 1H), 3.60 (dd, J=9.2,7.6Hz, 1H), 3.44 (dd, J=14.0,4.0Hz, 1H), 2.92-2.61(m,4H)；13C NMR(101MHz,CDCl3):δ160.0,156.1, 142.5,141.3,139.2,138.7, 138.3,136.0,130.6,130.0,129.2,128.4,128.2,126.9, 126.1,125.9,122.8,122.1, 121.6,120.6,120.0,118.8,116.8,108.3,77.2,65.8,56.7, 42.3,25.3；HRMS(EI) calculated for[C32H28N4]+requires m/z 468.2314,found m/z 468.2314。
Embodiment 17
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0919g, 0.10mmol), dppf (0.1087g, 0.20mmol) and toluene (10.0mL), are stirred at room temperature 10 minutes, after successively into bottle plus Enter 2- methyl-8-aminoquinolines (2-2) (0.3164g, 2.0mmol), (S) -2- (2- iodophenyls) -4- benzyl -4,5- dihydros - Thiazoline (3-9) (0.7650g, 2.0mmol) and NaOtBu (0.3868g, 4.0mmol) is replaced 3 times, 110 DEG C of reflux with nitrogen React 60h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, dichloromethane is washed, and filtrate is concentrated into no liquid stream Go out, silica gel column chromatography (PE/EA=10/1, v/v) separation (Rf=0.8) obtain product as light yellow solid 1-16 (0.4751g, 58% yield).1H NMR(400 MHz,CDCl3):δ 11.86 (s, 1H), 7.98 (d, J=8.4Hz, 1H), 7.86 (d, J= 8.4Hz, 1H), 7.78 (d, J=7.6Hz, 1H), 7.65 (d, J=8.0Hz, 1H), 7.41-7.31 (m, 2H), 7.30-7.19 (m, 4H), 7.18-7.01 (m, 3H), 6.86 (dd, J=7.6,7.2Hz, 1H), 5.20-5.02 (m, 1H), 3.46 (dd, J= 13.2,4.4Hz, 1H), 3.24 (dd, J=10.8,8.0Hz, 1H), 3.06 (dd, J=10.8,7.6Hz, 1H), 2.93 (dd, J =13.2,9.2Hz, 1H), 2.74 (d, 3H)；13C NMR(101MHz,CDCl3):δ167.4, 156.7,142.6,139.9, 138.5,138.4,136.1,132.6,131.2,129.2,128.3,127.3,126.3, 125.7,122.2,119.1, 118.5,115.8,111.7,79.3,40.6,35.8,25.6；HRMS(EI)calculated for[C26H23N3S]+ requires m/z 409.1613,found m/z 409.1620.
Embodiment 18
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0915g,0.10 Mmol), dppf (0.1096g, 0.20mmol) and toluene (10.0mL), are stirred at room temperature 10 minutes, after 2- is added into bottle successively Methyl-8-aminoquinoline (2-2) (0.3186g, 2.0mmol), (S) -2- (2- iodophenyls) -4- tertiary butyl -4,5- dihydro-thiazols Quinoline (3-10) (0.6914g, 2.0mmol) and NaOtBu (0.3837g, 4.0 mmol) is replaced 3 times with nitrogen, and 110 DEG C of reflux are anti- Answer 60h.Stopping heating, restores to room temperature after reaction solution, silica gel filtering, dichloromethane is washed, and filtrate is concentrated into no liquid outflow, Silica gel column chromatography (PE/EA=10/1 is gone out, v/v) separation (Rf=0.8) obtain product as light yellow solid 3-10 (0.6984g, 93% yield).1H NMR(400MHz,CDCl3):δ 11.18 (s, 1H), 7.97 (d, J=8.4Hz, 1H), 7.81-7.71 (m, 2H), 7.65 (dd, J=8.0,1.6Hz, 1H), 7.38-7.22 (m, 4H), 6.91-6.72 (m, 1H), 4.44 (dd, J= 11.2,8.4Hz, 1H), 3.21 (dd, J=10.8,8.8Hz, 1H), 3.10 (dd, J=11.6,10.8Hz, 1H), 2.71 (s, 3H),1.08(s,9H)；13C NMR(101MHz,CDCl3):δ166.6,157.1,143.0,140.3, 138.6,136.0, 132.5,130.8,127.4,125.5,122.4,119.2,118.6,115.9,114.0,88.8,35.1, 32.5,27.1, 25.4；HRMS(EI)calculated for[C23H25N3S]+requires m/z 375.1769, found m/z 375.1782.
Embodiment 19
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0913g, 0.10mmol), dppf (0.1087g, 0.20mmol) and toluene (10.0mL), are stirred at room temperature 10 minutes, after successively into bottle plus Enter 2- methyl-8-aminoquinolines (2-2) (0.3173g, 2.0mmol), (S) -2- (2- iodophenyls) -4- isopropyls -4,5- bis- Hydrogen-thiazoline (3-11) (0.6648g, 2.0mmol) and NaOtBu (0.3834g, 4.0 mmol), with nitrogen replace 3 times, 110 DEG C back flow reaction 60h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, dichloromethane is washed, and filtrate is concentrated into nothing Liquid flow, silica gel column chromatography (PE/EA=10/1 is gone out, v/v) separation (Rf=0.8) obtain product as light yellow solid 1-18 (0.6362g, 88% yield).1H NMR(400MHz,CDCl3):δ 11.45 (s, 1H), 7.98 (d, J=8.4Hz, 1H), 7.81 (d, J=8.4 Hz, 1H), 7.76 (d, J=7.6Hz, 1H), 7.69-7.61 (m, 1H), 7.38-7.26 (m, 4H), 6.89- 6.83 (m, 1H), 4.59-4.48 (m, 1H), 3.32 (dd, J=10.8,8.4Hz, 1H), 3.05 (dd, J=10.4,10.4Hz, 1H), 2.74 (s, 3H), 2.20-2.07 (m, 1H), 1.14 (d, J=6.8Hz, 3H), 1.04 (d, J=6.8Hz, 3H)；13C NMR(101MHz,CDCl3):δ166.6,157.0,142.8,140.2,138.6,136.1,132.6, 130.9,127.3, 125.6,122.3,119.3,118.9,118.6,116.0,113.0,85.0,34.2,33.4,25.4, 20.1,19.4；HRMS (EI)calculated for[C22H23N3S]+requires m/z 361.1613,found m/z 361.1618.
Embodiment 20
Under nitrogen protection, in super dry 50mL-Schlenk pipes, Pd is sequentially added2(dba)3(0.0922g, 0.10mmol), dppf (0.1087g, 0.20mmol) and toluene (10.0mL), are stirred at room temperature 10 minutes, after successively into bottle plus Enter 2- methyl-8-aminoquinolines (2-2) (0.3165g, 2.0mmol), (S) -2- (2- iodophenyls) -4- phenyl -4,5- dihydros - Thiazoline (3-12) (0.7352g, 2.0mmol) and NaOtBu (0.3882g, 4.0 mmol) is replaced 3 times with nitrogen, and 110 DEG C are returned Stream reaction 48h.Stop heating, restore to room temperature after reaction solution, silica gel filtering, dichloromethane is washed, and filtrate is concentrated into no liquid Outflow, silica gel column chromatography separation (Rf=0.8) (PE/EA=10/1 is gone out) obtain yellow solid product 1-19 (0.4615g, 58% yield).1H NMR (400MHz,CDCl3):δ 11.88 (s, 1H), 7.92 (d, J=8.4Hz, 1H), 7.88 (d, J= 8.4Hz, 1H), 7.81-7.72 (m, 2H), 7.50-7.46 (m, 2H), 7.40-7.23 (m, 6H), 7.15 (d, J=8.4Hz, 1H), 6.95-6.86 (m, 1H), 5.86 (dd, J=10.4,8.4Hz, 1H), 3.72 (dd, J=10.8,8.4Hz, 1H), 3.19 (dd, J=10.8,10.8Hz, 1H), 2.19 (s, 3H)；13C NMR(101MHz,CDCl3):δ168.8, 157.0, 142.7,142.4,139.7,138.5,135.9,132.6,131.4,128.4,127.3,127.1,126.8, 125.6, 122.2,119.4,118.6,118.4,116.2,111.4,81.4,39.9,24.6；HRMS(EI)calculated for [C25H21N3S]+requires m/z 395.1456,found m/z 395.1456.
Chiral quinoline aminated compounds and MXnThe alkene of complexes ira situ catalysis and the asymmetric reduction of pinacol borine are anti- It answers
Embodiment 21：(S) -2- (1- phenethyls) -4,4,5,5- tetramethyl -1,3,2- dioxy boron pentanes
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real 1-4 (0.03mmol), the toluene 1mL for applying the preparation of 4 method of example, after 2h is stirred at room temperature, sequentially add pinacol borine (HBpin) (90 μ L, 0.6mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel filters, and is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography： Ethyl acetate=50:1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 31% yield, 59.6%ee,1H NMR (400MHz,CDCl3) δ 7.29-7.18 (m, 4H), 7.16-7.10 (m, 1H), 2.43 (q, J= 7.6Hz, 1H), 1.33 (d, J=7.2Hz, 3H), 1.21 (s, 6H), 1.20 (s, 6H)；13C NMR(101MHz,CDCl3)δ 144.9,128.3,127.7,125.0,83.2,24.60,24.55,17.0.
Embodiment 22
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real Apply 5 method of example preparation 1-5 (0.03mmol), toluene 1mL, after 2h is stirred at room temperature, sequentially add HBpin (90 μ L, 1.2mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1 mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel Filtering, is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50: 1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 52% yield, 63.2%ee.
Embodiment 23
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real Apply 6 method of example preparation 1-6 (0.03mmol), toluene 1mL, after 2h is stirred at room temperature, sequentially add HBpin (90 μ L, 0.6mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1 mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel Filtering, is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50: 1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 37% yield, 50%ee.
Embodiment 24
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real Apply 7 method of example preparation 1-7 (0.03mmol), toluene 1mL, after 2h is stirred at room temperature, sequentially add HBpin (90 μ L, 0.6mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1 mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel Filtering, is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50: 1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 37% yield, 52%ee.
Embodiment 25
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real Apply 8 method of example preparation 1-8 (0.03mmol), toluene 1mL, after 2h is stirred at room temperature, sequentially add HBpin (90 μ L, 0.6mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1 mol/L, solvent THF), 50 DEG C of stirring 1h.Reaction solution silica gel Filtering, is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50: 1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 34% yield, 57%ee.
Embodiment 26
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real Apply 9 method of example preparation 1-9 (0.03mmol), toluene 1mL, after 2h is stirred at room temperature, sequentially add HBpin (90 μ L, 0.6mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1 mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel Filtering, is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50: 1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 34% yield, 64%ee.
Embodiment 27
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0032g, 0.025 mmol), it is real Apply 11 method of example preparation 1-11 (0.03mmol), toluene 1mL, after 2h is stirred at room temperature, sequentially add HBpin (90 μ L, 0.6mmol), styrene (0.5mmol), NaBHEt3(75 μ L, 1 mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel Filtering, is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50: 1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 41% yield, 65%ee,1H NMR (400MHz, CDCl3) δ 7.29-7.18 (m, 4H), 7.16-7.10 (m, 1H), 2.43 (q, J=7.6Hz, 1H), 1.33 (d, J =7.2Hz, 3H), 1.21 (s, 6H), 1.20 (s, 6H)
Embodiment 28
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 4 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-4 (0.03mmol) prepared by method, ether (1.0mL), and styrene (1.0mmol), frequency are added afterwards That alcohol borine (1.2mmol) then stirs 72 hours at 0 DEG C.Reaction solution silica gel filters, and is washed with ether, cleaning solution is concentrated into No liquid flows out, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) separation (Rf=0.8) obtains product 6-1.Oily liquids, 40% yield
Embodiment 29
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 5 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-5 (0.03mmol) prepared by method, ether (1.0mL), and styrene (1.0mmol), frequency are added afterwards That alcohol borine (1.2mmol), is then stirred at room temperature 18 hours.Reaction solution silica gel filters, and is washed with ether, cleaning solution is concentrated into No liquid flows out, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) separation (Rf=0.8) obtains product 6-1.Oily liquids, 42% yield, 89%ee.
Embodiment 30
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 7 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-7 (0.03mmol) prepared by method, ether (1.0mL), and styrene (1.0mmol), frequency are added afterwards That alcohol borine (1.2mmol), is then stirred at room temperature 18 hours.Reaction solution silica gel filters, and is washed with ether, cleaning solution is concentrated into No liquid flows out, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) separation (Rf=0.8) obtains product 6-1.Oily liquids, 68% yield, 72%ee.
Embodiment 31
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), embodiment 11 is added in the reaction tube of a drying 10min is stirred at room temperature in 1-11 (0.03mmol) prepared by method, ether (1.0mL), and styrene (1.0mmol) is added afterwards, Pinacol borine (1.2mmol) is then stirred at room temperature 18 hours.Reaction solution silica gel filters, and is washed with ether, cleaning solution concentration It is flowed out to no liquid, (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) separation (Rf=0.8) is produced Object 6-1.Oily liquids, 38% yield, 79.2%ee.
Embodiment 32
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), embodiment 11 is added in the reaction tube of a drying 10min is stirred at room temperature in 1-11 (0.03mmol) prepared by method, ether (1.0mL), rear that 4- methoxy styrenes are added (1.0mmol), pinacol borine (1.2mmol) are then stirred at room temperature 18 hours.Reaction solution silica gel filters, and uses ether It washes, cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=20:1, v/v) it detaches (Rf=0.7) product 6-2 is obtained.Oily liquids, 38% yield, 76%ee,1H NMR(400MHz,CDCl3):δ7.36-7.26 (m, 2H), 6.95-6.80 (m, 2H), 4.85 (q, J=6.4Hz, 1H), 3.80 (s, 3H), 1.85 (s, 1H), 1.47 (d, J= 6.4Hz, 3H)；13C NMR(101MHz,CDCl3):δ159.0,138.0,126.6,113.8,69.9,55.3,25.0.
Embodiment 33
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 5 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-5 (0.03mmol) prepared by method, ether (1.0mL), rear that 4- acetoxy-styrenes are added (1.0mmol), pinacol borine (1.2mmol) are then stirred at room temperature 18 hours.Reaction solution silica gel filters, and is washed with ether, Cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) (Rf=is detached 0.5) product 6-3 is obtained.Oily liquids, 56% yield, 80%ee,1H NMR(400MHz,CDCl3) δ 7.21 (d, J=8.0Hz, 2H), 6.99-6.94 (m, 2H), 2.43 (q, J=7.6Hz, 1H), 2.27 (s, 3H), 1.31 (d, J=7.6Hz, 3H), 1.21 (s,6H),1.20(s,6H)；13C NMR(101MHz,CDCl3)δ169.6,148.2,142.4,128.5, 121.1,83.3, 24.53,24.50,21.1,17.0.HRMS(EI)calculated for[C16H23BO4]+requires m/z 290.1689, found m/z 290.1694.
Embodiment 34
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 4 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-4 (0.03mmol) prepared by method, ether (1.0mL), rear that 4- fluorobenzene ethenes are added (1.0mmol), pinacol borine (1.2mmol) are then stirred at room temperature 18 hours.Reaction solution silica gel filters, and uses ether It washes, cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) it detaches (Rf=0.8) product 6-4 is obtained.Oily liquids, 66% yield, 79%ee.
1H NMR(400MHz,CDCl3) δ 7.20-7.12 (m, 2H), 7.00-6.86 (m, 2H), 2.41 (q, J=7.6 Hz, 1H), 1.30 (d, J=7.6Hz, 3H), 1.21 (s, 6H), 1.20 (s, 6H)
Embodiment 35
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 7 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-7 (0.03mmol) prepared by method, ether (1.0mL), rear that 3- methyl styrenes are added (1.0mmol), pinacol borine (1.2mmol) are then stirred at room temperature 18 hours.Reaction solution silica gel filters, and uses ether It washes, cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) it detaches (Rf=0.8) product 6-5 is obtained.Oily liquids, 69% yield, 89%ee.1H NMR(400MHz,CDCl3) δ 7.15 (t, J= 7.6Hz, 1H), 7.05-6.99 (m, 2H), 6.94 (d, J=7.6Hz, 1H), 2.39 (q, J=7.6Hz, 1H), 2.31 (s, 3H), 1.31 (d, J=7.6Hz, 3H), 1.21 (s, 6H), 1.20 (s, 6H)；13C NMR(101MHz,CDCl3)δ144.8, 137.7, 128.6,128.1,125.8,124.8,83.2,24.6,24.5,21.4,17.1.HRMS(EI)calculated for [C15H23BO2]+requires m/z 246.1791,found m/z 246.1795.
Embodiment 36
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 5 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-5 (0.03mmol) prepared by method, ether (1.0mL), rear that 3- fluorobenzene ethenes are added (1.0mmol), pinacol borine (1.2mmol) are then stirred at room temperature 18 hours.Reaction solution silica gel filters, and uses ether It washes, cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) it detaches (Rf=0.8) product 6-6 is obtained.Oily liquids, 70% yield, 80%ee.
1H NMR(400MHz,CDCl3)δ7.23-7.16(m,1H),7.00-6.90(m,2H),6.85-6.75(m, 1H), 2.49-2.37 (m, 1H), 1.32 (d, J=7.2Hz, 3H), 1.21 (s, 6H), 1.20 (s, 6H)
Embodiment 37
Under nitrogen protection, at room temperature, cobalt acetate (0.025mmol), 5 side of embodiment is added in the reaction tube of a drying 10min is stirred at room temperature in 1-5 (0.03mmol) prepared by method, ether (1.0mL), rear that 3- chlorostyrenes are added (1.0mmol), pinacol borine (1.2mmol) are then stirred at room temperature 18 hours.Reaction solution silica gel filters, and uses ether It washes, cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography：Ethyl acetate=50:1, v/v) it detaches (Rf=0.8) product 6-7 is obtained.Oily liquids, 62% yield, 82%ee.
1H NMR(400MHz,CDCl3) δ 7.23-7.15 (m, 2H), 7.13-7.06 (m, 2H), 2.41 (q, J=7.2 Hz, 1H), 1.31 (d, J=7.2Hz, 3H), 1.21 (s, 6H), 1.20 (s, 6H)
Embodiment 38
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0016g, 0.0125 mmol), 1-16 (0.015mmol) prepared by 16 method of embodiment, Isosorbide-5-Nitrae-dioxane 0.5mL after 2h is stirred at room temperature, sequentially add Styrene (0.5mmol), HBpin (90 μ L, 0.6mmol), NaBHEt3(25 μ L, 1mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel filters, and is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography： Ethyl acetate=50:1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 78% yield, 79% ee.
Embodiment 39
Under nitrogen protection, FeCl is sequentially added in super dry 25mL-Schlenk pipes2(0.0016g, 0.0125 mmol), 1-18 (0.015mmol) prepared by 18 method of embodiment, Isosorbide-5-Nitrae-dioxane 0.5mL after 2h is stirred at room temperature, sequentially add Styrene (0.5mmol), HBpin (90 μ L, 0.6mmol), NaBHEt3(25 μ L, 1mol/L, solvent THF), is stirred at room temperature 18h.Reaction solution silica gel filters, and is washed with ether, and cleaning solution is concentrated into no liquid outflow, and (eluant, eluent is petroleum ether to silica gel column chromatography： Ethyl acetate=50:1, v/v) separation (Rf=0.8) obtains geneva hydroboration product 6-1.Oily liquids, 29% yield, 74.2%ee.

Claims (10)

1. chiral quinoline amine compounds shown in a kind of formula (1),
* in formula (1) represents asymmetric carbon atom；
X is O, S or NR in formula (1)14；
R1, R2, R3, R4, R5, R6, R7, R8, R9And R10Respectively stand alone as hydrogen, halogen, the alkyl of C1-C10, C1-C4 fluoroalkyl, The aryl of the alkoxy of C1-C4, the naphthenic base of C3~C10 or C6-C14；
R11With R12Respectively stand alone as the aryl of hydrogen, the alkyl of C1-C10 or C6-C14；
R13For the alkyl of C1-C12, the aryl of the naphthenic base of C3~C12, benzyl or C6-C14, the wherein H on the alkyl of C1-C12 It is not substituted or is replaced by the alkoxy of 1-2 C1-C4；H in the naphthenic base of the C3~C12 is not substituted or by 1-3 The alkoxy of C1-C4 alkyl or C1-C4 replace, and the H on the aryl of the C6-C14 is unsubstituted or is taken by 1-3 substituent A Generation, the substituent A be the alkyl of C1-C4, the alkoxy of C1-C4, the fluoroalkyl of C1-C4, the Fluoroalkyloxy of C1-C4, F or Cl；
R14For hydrogen, the aryl of the alkyl of C1-C10, benzyl or C6-C14, the H on the aryl of the C6-C14 it is unsubstituted or by 1-4 substituent B substitutions, the substituent B are fluoroalkyl, the C1-C4 of the alkyl of C1-C4, the alkoxy of C1-C4, C1-C4 Fluoroalkyloxy, F or Cl；
Or R12With R13It connect cyclization with two carbon on five-membered ring, forms C9-C15Benzo naphthenic base.
2. chirality quinoline amine compounds as described in claim 1, it is characterised in that the R1-R10Respectively stand alone as hydrogen, C1-C6 Alkyl, the naphthenic base of C3~C10, the alkoxy of C1~C4 or C6-C10 aryl；
R11With R12The respectively aryl of hydrogen, the alkyl of C1-C6 or C6-C14；
R13For the aryl of the alkyl of C1-C6, benzyl or C6-C10；
R14For hydrogen, the aryl of the alkyl of C1-C6, benzyl or C6-C10.
3. chirality quinoline amine compounds as described in claim 1, it is characterised in that the quinoline amine compounds are one of following：
4. the preparation method of chiral quinoline amine compounds described in a kind of claim 1, it is characterised in that the method is：
Under inert gas environment, in the presence of transition-metal catalyst and ligand, alkali, in organic solvent A, with shown in formula (2) Aminoquinoline and formula (3) shown in halides be raw material or with benzene shown in quinoline halides shown in formula (4) and formula (5) Amine is that raw material carries out coupling reaction, and quinoline aminated compounds shown in formula (1) is made；The transition-metal catalyst is the complexing of Pd Object；The ligand is organic phosphorus compound；The alkali is the alkali metal salt of alcohol；
X is O, S or NR in formula (3)14；Y is F, Cl, Br or I；
X is O, S or NR in formula (5)14；Y is F, Cl, Br or I in formula (4)；
R in formula (2)1, R2, R3, R4, R5, R6, R7, R8, R9And R10Respectively stand alone as hydrogen, halogen, the alkyl of C1-C10, C1-C4 The aryl of fluoroalkyl, the alkoxy of C1-C4, the naphthenic base of C3~C10 or C6-C14；
R11With R12Respectively stand alone as the aryl of hydrogen, the alkyl of C1-C10 or C6-C14；
R13For the alkyl of C1-C12, the aryl of the naphthenic base of C3~C12, benzyl or C6-C14, the wherein H on the alkyl of C1-C12 It is not substituted or is replaced by the alkoxy of 1-2 C1-C4；H in the naphthenic base of the C3~C12 is not substituted or by 1-3 The alkoxy of C1-C4 alkyl or C1-C4 replace, and the H on the aryl of the C6-C14 is unsubstituted or is taken by 1-3 substituent A Generation, the substituent A be the alkyl of C1-C4, the alkoxy of C1-C4, the fluoroalkyl of C1-C4, the Fluoroalkyloxy of C1-C4, F or Cl；
Or R12With R13It connect cyclization with two carbon on five-membered ring, forms C9-C15Benzo naphthenic base；
R14For hydrogen, the aryl of the alkyl of C1-C10, benzyl or C6-C14, the H on the aryl of the C6-C14 it is unsubstituted or by 1-4 substituent B substitutions, the substituent B are fluoroalkyl, the C1-C4 of the alkyl of C1-C4, the alkoxy of C1-C4, C1-C4 Fluoroalkyloxy, F or Cl；
R in formula (3), formula (4) and formula (5)1-R14Same formula (2).
5. preparation method as claimed in claim 4, it is characterised in that the reaction temperature of the coupling reaction is 50 DEG C to 200 DEG C, the reaction time is 1 hour to 72 hours.
6. preparation method as claimed in claim 4, it is characterised in that the organic solvent A is benzene, dimethylformamide, four Any one in chlorination carbon, toluene, petroleum ether, dioxane, tetrahydrofuran, ether, chloroform, dimethylbenzene or acetonitrile； The transition-metal catalyst is Pd2(dba)3Or Pd (dba)2；The ligand is 1,1'Bis- (diphenylphosphine) ferrocene, (±)-2,2'Double-(diphenyl phosphine) -1,1'Dinaphthalene or the bis- diphenylphosphine -9,9- xanthphos of 4,5-；The alkali is Sodium tert-butoxide or potassium tert-butoxide.
7. preparation method as claimed in claim 4, which is characterized in that amino shown in halides, formula (2) shown in formula (3) The ratio between amount of substance of quinoline, transition-metal catalyst, ligand, alkali is 1:0.1-4:0.01-0.5:0.01-0.5：1~4；Formula (4) quinoline bromo-derivative shown in, the ratio between amount of substance of aniline, transition-metal catalyst, ligand, alkali shown in formula (5) are 1: 0.1-4:0.01-0.5:0.01-0.5：1~4.
8. chiral quinoline amine compounds are in preparing chiral organic boron ester compounds shown in formula (1) described in claim 1 Using.
9. application as claimed in claim 8, it is characterised in that the method for the application is：In organic solvent B, transition metal Compound MYnIn the presence of quinoline amine compounds shown in formula (1), with aromatic olefin compound shown in formula (7) and formula (8) institute The pinacol borine shown is that raw material carries out asymmetric geneva hydroboration, and chiral organic boron ester shown in formula (6) is prepared Compound；
In formula (7), Ar is phenyl or substituted-phenyl, and the substituent group of the substituted-phenyl is the alcoxyl of the alkyl of C1-C6, C1-C6 Base, methyl mercapto, CF3, F, Cl or Br；The same formulas of Ar (7) in formula (6)；
The transistion metal compound MYnMiddle M is transition-metal Fe or Co；Y is F, Cl, Br, I, OSO2CH3、OSO2CF3、O (CH3) C=CHCOCH3、OCOCH2CH3、OCOCH3、ClO4In any one；N is the number of Y, is 2 or 3.
10. application as claimed in claim 9, it is characterised in that the transistion metal compound MYnFor frerrous chloride or second Sour cobalt；The organic solvent B is toluene, ether or Isosorbide-5-Nitrae-dioxane.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013096151A1 (en) * 2011-12-22 2013-06-27 Glaxosmithkline Llc Chemical compounds
CN105693647A (en) * 2016-01-11 2016-06-22 浙江大学 Chiral compounds containing imine oxazoline amine and preparing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013096151A1 (en) * 2011-12-22 2013-06-27 Glaxosmithkline Llc Chemical compounds
CN105693647A (en) * 2016-01-11 2016-06-22 浙江大学 Chiral compounds containing imine oxazoline amine and preparing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XU CHEN ET AL.: ""Iminophenyl Oxazolinylphenylamine for Enantioselective Cobalt-Catalyzed Hydrosilylation of Aryl Ketones"", 《ORGANIC LETTERS》 *

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