CN109529940A - Diphenylamines-phosphine-oxazoline ligand, its synthetic method and its metal complex and purposes - Google Patents

Diphenylamines-phosphine-oxazoline ligand, its synthetic method and its metal complex and purposes Download PDF

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CN109529940A
CN109529940A CN201811512964.9A CN201811512964A CN109529940A CN 109529940 A CN109529940 A CN 109529940A CN 201811512964 A CN201811512964 A CN 201811512964A CN 109529940 A CN109529940 A CN 109529940A
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phosphine
diphenylamines
room temperature
oxazoline
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CN109529940B (en
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陈建辉
夏远志
高克成
倪扬威
况锦强
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Wenzhou University
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Abstract

The present invention provides diphenylamines-phosphine-oxazoline ligand, be compound described in formula (1) or be formula (1) compound enantiomer or raceme, wherein R1And R2Respectively C1~C10Alkyl, benzyl, one of phenyl or substituted phenyl, heteroaryl.Diphenylamines-phosphine-oxazoline ligand can be independently used for preparation chirality or achirality organic compound, stable metal complex can also be formed with transition-metal Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, the metal complex can be applied to asymmetric catalysis, especially have very high catalytic activity to the asymmetric hydrogenation of alkene and ketone.The present invention also provides two efficient synthetic routes, and three step gross production rates are 60% or more.

Description

Diphenylamines-phosphine-oxazoline ligand, its synthetic method and its metal complex and purposes
Technical field
The present invention relates to catalyst technical field more particularly to diphenylamines-phosphine-oxazoline ligand, its synthetic method and its Metal complex and purposes.
Background technique
Transition metal-catalyzed asymmetric catalysis synthesis is to prepare one of chipal compounds mode the most efficient and work The popular domain that industry and academia pay close attention to jointly.Since chemists have found that transition can be adjusted by the combination of chiral ligand After activity and selectivity of the metal in asymmetric catalysis, the design of chiral ligand just become it is transition metal-catalyzed not One of the core content in symmetrical synthesis field.So far have thousands of chiral ligands to be developed applied to asymmetric conjunction At reaction, wherein also having emerged in large numbers some advantage chiral ligand [(a) Q.Zhou, Privileged with extensive catalytic activity Chiral Ligands and Catalysts,Wiley-VCH,Weinheim,2011；b)T.P.Yoon,E.N.Jacobsen, Science 2003,299,1691；c)A.faltz,W.J.Drury III,PNAS2004,101,5723.].Chiral oxazoline Can be prepared by the common amino acid of nature, be a kind of common chiral ligand building block, as advantage chiral ligand PyBox, BOX, PHOX etc., can with many metals formed many types of complex catalysis reaction [(a) D.Rechavi, M.Lemaire, Chem.Rev.2002,102,346；(b)G.Desimoni,G.Faita,P.Quadrelli,Chem.Rev.2003,103, 3119.].Therefore, the broad interest that different chiral ligand skeletons causes chemist is constructed based on oxazoline building block, It is thus achieved that the efficient asymmetry catalysis conversion of some column, pushed asymmetric catalysis field development [(a) S.Zhu, X.Song,Y.Li,Y.Cai,Q.Zhou,J.Am.Chem.Soc.2010,132,16374；(b)Y.Zhang,F.Wang, W.Zhang,J.Org.Chem.2007,72,9208；(c)B.Cheng,W.Liu,Z.Lu,J.Am.Chem.Soc.2018,140, 501；(d)J.Guo,B.Cheng,X.Shen,Z.Lu,J.Am.Chem.Soc.2017,139,15316.].
Asymmetric hydrogenation has many advantages, such as that Atom economy is high, easy to operate, cleaning is green, is most important organic One of reaction is always academic and industry research emphasis and hot spot, and is used widely in the industrial production.At present not The catalyst of symmetric hydrogenation reaction is based primarily upon the platinum-group noble metals such as rhodium, ruthenium, iridium, palladium, and platinum group metal reserves in the earth's crust are less (amounting to workable reserves is only 7.1 ten thousand tons), belongs to strategic resources.Moreover, the 99% of platinum group metal reserves concentrate on South Africa, The four countries such as Russia, the U.S., Canada.China is rare one of the country in platinum group metal, with the development of economy, platinum group metal Imbalance between supply and demand it is increasingly sharp, 90% or more platinum group metal consumption demand relies on import [a) global Platinum metals resources in recent years And the simple analysis of platinum, palladium, rhodium state between supply and demand, resource and industry, 2012,14,138；B) establishment of platinum family OPEC and the challenge to China, China Metal Bulletin, 2014,10,8；C) 2014 Chinese noble metal meter, gold, 2014,7,1.].Meanwhile platinum group metal is for life It is poisonous and harmful to order body, needs its residual quantity in finished industrial product of strict control, greatly limits it in drug and fine chemistry industry The application in field.
Therefore, based on the earth such as iron and cobalt high yield transition metal, a kind of new diphenylamines-phosphine-oxazoline ligand, hair are developed Efficient asymmetric hydrogenation is opened up, not only there is urgent researching value, it may have good economic benefit and industrial application Potentiality, where this power exactly of the invention being accomplished and basis.
Summary of the invention
In order to overcome the defect of the prior art as indicated above, the present inventor has made intensive studies this, is paying After a large amount of creative works, so as to complete the present invention.
Specifically, the technical problems to be solved by the present invention are: providing diphenylamines-phosphine-oxazoline ligand, its synthesis side Method and its metal complex and purposes, to provide the catalyst that can realize high synthetic yield by a plurality of synthetic line, and really Protecting has very high catalytic activity in its asymmetric hydrogenation to alkene and ketone.
In order to solve the above technical problems, the technical scheme is that
In a first aspect, being compound described in formula (1) the present invention provides diphenylamines-phosphine-oxazoline ligand
It or is the enantiomer or raceme of formula (1) described compound, wherein
R1And R2Respectively C1~C10Alkyl, benzyl, phenyl or substituted phenyl (substituent group C1~C6Alkyl, hydrocarbon Oxygroup and halohydrocarbyl, substituent group quantity are one of 1-5), heteroaryl.
Wherein, the alkyl be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, N-pentyl, cyclopenta, n-hexyl, cyclohexyl etc..
In the present invention, as a kind of perferred technical scheme, R1Preferably methyl, ethyl, n-propyl, isopropyl, positive fourth One of base, isobutyl group, sec-butyl, tert-butyl, phenyl or benzyl.
In the present invention, as a kind of perferred technical scheme, R2Preferably cyclohexyl or phenyl.
Second aspect, the present invention provides a kind of synthetic method of above-mentioned diphenylamines-phosphine-oxazoline ligand, including it is as follows Step:
Under room temperature, inert atmosphere, dimethyl sulfoxide (DMSO) solvent, neighbour Iodoaniline (A) He Shuding is added in S1 in reactor Potassium alcoholate, ten minutes later, reactor is transferred to dropwise addition o Flurobenzonitrile (B) at -10 DEG C for stirring, continues reacting at room temperature after completion of dropwise addition Isolated intermediate 2- (2- iodophenyl) amido cyanophenyl (C) after (1-2 hours) for a period of time.
Wherein, the molar ratio of adjacent Iodoaniline, o Flurobenzonitrile and potassium tert-butoxide is (1~10): (1~10): (1 in step S1 ~10)；Preferably 1:1.2:2.
Solvent, 2- (2- iodophenyl) amido cyanophenyl (C), amido alcohol (D), catalyst is added at room temperature in S2 in reactor, Then raise temperature to reflux, the isolated iodo- 2 '-oxazolines-diphenylamines (E) of intermediate 2- after reaction a period of time (3-4 days).
Wherein, solvent described in step S2 is organic solvent, is polarity or nonpolar solvent, the organic solvent is Benzene, toluene, chlorobenzene, dimethylbenzene, carbon tetrachloride, petroleum ether, tetrahydrofuran, dimethylformamide, ether, methylene chloride, trichlorine Methane, hexamethylene, n-hexane, normal heptane, dioxane, any one in acetonitrile；Preferably toluene or chlorobenzene.
Wherein, the step S2 reaction catalyst is selected from zinc chloride, trifluoromethayl sulfonic acid zinc, aluminium chloride, iron chloride, three One of fluorine copper methane sulfonate, silver trifluoromethanesulfonate；Preferably from zinc chloride or trifluoromethayl sulfonic acid zinc.
Wherein, catalyst, 2- described in step S2 (2- iodophenyl) amido cyanophenyl (C) and the molar ratio of amido alcohol (D) are 1:(1~10000): (1~10000)；Preferably 1:(10~100): (10~100).
S3 is added cuprous iodide, two replaces phosphine hydrogen, dimethyl-ethylenediamine and first under room temperature, inert atmosphere, in reactor Benzene is stirred at room temperature and intermediate E and Cs is added after ten minutes2CO3, isolated product 1 after being warming up to back flow reaction for a period of time, Diphenylamines-phosphine-oxazoline ligand as of the present invention.
Wherein, cuprous iodide, dimethyl-ethylenediamine, Cs in step S32CO3, two replace phosphine hydrogen and intermediate E molar ratio For 1:(1~100): (1~10000): (1~10000): (1~10000)；Preferably 1:7:(40~100): (20~100): (20~100).
Its synthetic route is as follows:
The present invention provides another synthetic methods of above-mentioned diphenylamines-phosphine-oxazoline ligand, include the following steps:
The first step, be added under room temperature, inert atmosphere, in reactor cuprous iodide, two replace phosphine hydrogen, dimethyl-ethylenediamine and Toluene is stirred at room temperature and adjacent Iodoaniline (A) and Cs is added after ten minutes2CO3, it is warming up to back flow reaction (10-12 hours) for a period of time Isolated intermediate 2- bis- replaces phosphino- aniline (F) afterwards.
Wherein, cuprous iodide, dimethyl-ethylenediamine, Cs in the first step2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:(1 ~100): (1~10000): (1~10000): (1~10000)；Preferably 1:7:(40~100): (20~100): (20~ 100)。
Dimethyl sulfoxide, intermediate F and potassium tert-butoxide is added at room temperature in second step in reactor, stir after ten minutes, Reactor, which is transferred at -10 DEG C, is added dropwise o Flurobenzonitrile, continues to divide after reacting at room temperature one (1-2 hours) time after completion of dropwise addition From obtaining intermediate 2- [2- (two replace phosphino-) phenyl] amido cyanophenyl G.
Wherein, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are (1~10): (1~10) in second step reaction: (1~10)；Preferably 1:1.2:2.
Step 3: solvent, intermediate G, amido alcohol, catalyst are added in reactor, then heats up under room temperature, air atmosphere To reflux, isolated product 1 after reaction a period of time (5 days), diphenylamines-phosphine-oxazoline ligand as of the present invention.
Wherein, solvent described in third step is organic solvent, is polarity or nonpolar solvent, the organic solvent is Benzene, toluene, chlorobenzene, dimethylbenzene, carbon tetrachloride, petroleum ether, tetrahydrofuran, dimethylformamide, ether, methylene chloride, trichlorine Methane, hexamethylene, n-hexane, normal heptane, dioxane, any one in acetonitrile；Preferably toluene or chlorobenzene.
Wherein, the third step reaction catalyst is selected from zinc chloride, trifluoromethayl sulfonic acid zinc, aluminium chloride, iron chloride, three One of fluorine copper methane sulfonate, silver trifluoromethanesulfonate；Preferably from zinc chloride or trifluoromethayl sulfonic acid zinc.
Wherein, the molar ratio of the third step reaction catalyst, intermediate G and amido alcohol is 1:(1~10000): (1 ~10000)；Preferably 1:(10~100): (10~100).
Its synthetic route is as follows:
The third aspect, the present invention provides diphenylamines-phosphine-oxazoline metal complex, the complex be by compound 1 with The transition metal salt of the periodic table of elements is formed, and has the general formula as described in formula (2)
Wherein, M is one of transition-metal Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, Ir；
X is selected from halide (F, Cl, Br, I), pseudohalide (cyanide, cyanic acid, salt, isocyanates), carboxylic acid, sulfonic acid, phosphine Acid anion (carbonate, formate, acetate, propionate, methane sulfonic acid root, trichloromethyl sulfonate radical, phenylbenzimidazole sulfonic acid root, Tosylate) in any one；
E is H or alkyl；
N1 is the number of X, is 0,1,2,3；
N2 is the number of E, is 0 or 1.
As described above, R1And R2Respectively C1~C10Alkyl, benzyl, phenyl or substituted phenyl (substituent group C1~ C6Alkyl, oxyl and halohydrocarbyl, substituent group quantity is 1-5), one of heteroaryl；Wherein, the alkyl is Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, cyclopenta, n-hexyl, hexamethylene Base etc..
R1Preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl or benzyl One of base.R2Preferably cyclohexyl or phenyl.
Fourth aspect, the present invention provides diphenylamines-phosphine-oxazoline metal complex purposes, refer to and utilize catalytic amount At least one diphenylamines-phosphine-oxazoline ligand or diphenylamines-phosphine-oxazoline metal complex as catalyst pass through catalysis Reaction prepares optical selective organic compound.
After above-mentioned technical proposal, the beneficial effects of the present invention are:
The present invention provides a kind of novel diphenylamines-phosphine-oxazoline ligand, can with transition-metal Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, Ir form stable metal complex, and it is anti-that which can be applied to asymmetry catalysis Answer, especially in the asymmetric hydrogenation of alkene and ketone have very high catalytic activity.The present invention also provides two Efficient synthetic route, three step gross production rates are 60% or more.
Purposes the present invention also provides metal complex as homogeneous catalyst, catalyst pass through the insatiable hungers such as alkene and ketone With the hydrogenation of compound, it can be used for preparing chiral or achirality organic compound, it can chirality prepared in accordance with the present invention Or achirality organic compound is active material or the intermediary for being used to prepare the substance, especially drug, fine chemical product, In terms of the production of pesticide etc..
Specific embodiment
Below with reference to specific embodiment, the present invention is further described.But the purposes and mesh of these exemplary embodiments Be only used to enumerate the present invention, any type of any restriction not is constituted to real protection scope of the invention, it is more non-to incite somebody to action this The protection scope of invention is confined to this.
Diphenylamines-phosphine-oxazoline ligand is compound described in formula (1)
It or is the enantiomer or raceme of formula (1) described compound, wherein R1And R2Respectively C1~C10Alkyl, benzyl Base, phenyl or substituted phenyl (substituent group C1~C6Alkyl, oxyl and halohydrocarbyl, substituent group quantity be 1-5), One of heteroaryl.
Embodiment 1
In the diphenylamines-phosphine-oxazoline ligand of the present embodiment, R1It is selected as methyl, R2It is selected as phenyl, structural formula are as follows:
Above-mentioned diphenylamines-phosphine-oxazoline ligand (1a) the preparation method is as follows:
S1: sequentially adding potassium tert-butoxide (20mmol, 2equiv.) under room temperature, nitrogen atmosphere, in reaction flask, dry DMSO (20mL) and adjacent Iodoaniline (10mmol, 1equiv.), obtains a dark solution.It is stirred at room temperature after ten minutes, reaction flask transfer To stirring in -10 DEG C of ice makers, o Flurobenzonitrile (12mmol, 1.2equiv.) is added under nitrogen atmosphere, i.e., adjacent Iodoaniline, o Flurobenzonitrile Molar ratio with potassium tert-butoxide is 1:1.2:2.
Reaction flask, which is transferred to, after completion of dropwise addition is stirred at room temperature reaction 2 hours.
100mL saturated salt solution and 50mL ethyl acetate, liquid separation are added after reaction；Water phase is extracted with ethyl acetate again Twice, merge organic phase, it is dry that anhydrous sodium sulfate is added.Filtering, it is solid that filtrate decompression rotary evaporation removing solvent obtains sepia Body is recrystallized to give intermediate C, yield 86% with dehydrated alcohol.
The testing result of intermediate C is as follows:
1H NMR:(399.9MHz,CDCl3) δ 7.88 (d, J=8.0Hz, 1H), 7.55 (dd, J=78.0,1.4Hz, 1H), 7.44-7.36 (m, 1H), 7.36-7.29 (m, 2H), 7.09 (d, J=8.5Hz, 1H), 6.96-6.89 (m, 1H), 6.89-6.81 (m,1H),6.39(br,1H)；13C NMR:(125.8MHz,CDCl3)δ13C NMR:(125.8MHz,CDCl3)δ146.4, 141.1,140.0,133.8,133.2,129.2,125.6,121.3,120.3,117.2,115.2,100.0,93.5；HRMS Calcd for[C13H9IN2+H]+:320.9883；found:320.9883.
S2: sequentially adding intermediate C (10mmol) under air atmosphere, in reaction flask, (S) -2 aminopropanol (D1) (12mmol), toluene (10mL), Zn (OTf)2(1mmol), i.e. catalyst, 2- (2- iodophenyl) amido cyanophenyl (intermediate C) and The molar ratio of amido alcohol (D1) is 1:10:12, is warming up to the 3 day time of back flow reaction.It is down to room temperature after reaction, silica gel is taken out Filter, filtrate decompression rotary evaporation remove solvent, and column chromatography for separation obtains intermediate E 1, yield 94%.The detection of intermediate E 1 As a result as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.54 (br, 1H), 7.88 (dd, J=8.0,1.4Hz, 1H), 7.81 (dd, J=8.0,1.4Hz, 1H), 7.46 (dd, J=8.2,1.4Hz, 1H), 7.31-7.21 (m, 2H), 7.21-7.15 (m, 1H), 6.83-6.73 (m, 2H), 4.53-4.42 (m, 2H), 3.94-3.85 (m, 1H), 1.39 (d, J=6.2Hz, 3H)；13C NMR: (125.8MHz,CDCl3)δ163.2,144.9,143.3,139.9,131.7,129.9,128.6,124.4,121.9,117.7, 113.7,111.3,94.1,72.5,62.1,21.5；HRMS Calcd for[C16H15IN2O+H]+:379.0302；found: 379.0306.
S3: CuI (0.5mmol), PPh are sequentially added under room temperature, nitrogen atmosphere, in reaction flask2PH (10.5mmol), dimethyl Ethylenediamine (3.5mmol) and toluene (20mL) are stirred at room temperature and intermediate E 1 (10mmol) and Cs are added after ten minutes2CO3 (20mmol), it may be assumed that cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and intermediate E 1 is replaced to be 1:7:40: 21:20 is warming up to back flow reaction 10 hours.
It is down to room temperature after reaction, silica gel filters, and filtrate decompression rotary evaporation removes solvent, and column chromatography for separation obtains pure Product 1a, yield 94%.
The testing result for the pure products 1a that the present embodiment obtains is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.28 (br, 1H), 7.69 (d, J=7.8Hz, 1H), 7.55-7.44 (m, 1H),7.40-7.20(m,11H),7.20-7.11(m,1H),7.11-7.04(m,1H),7.04-6.95(m,1H),6.90- 6.80 (m, 1H), 6.74-6.63 (m, 1H), 4.26 (dd, J=8.6,8.4Hz, 1H), 4.06-3.92 (m, 1H), 3.73 (dd, J =7.4,7.2Hz, 1H), 0.96 (d, J=5.6Hz, 3H)；13C NMR:(125.8MHz,CDCl3)δ163.0,146.1,144.8 (d, J=21.8Hz), 137.1 (d, J=7.2Hz), 137.0 (d, J=7.8Hz), 134.2,134.0,133.93,133.88, (133.77,132.3 d, J=11.4Hz), 131.5,129.6,129.4,128.6,128.44,128.41,128.36,124.2 (d, J=2.8Hz), 124.1,116.8,113.6,110.6,72.2,61.8,21.3；31P NMR(CDCl3,161MHz)δ- 16.3；HRMS Calcd for[C28H25N2OP+H]+:437.1777；found:437.1781.
Embodiment 2
In the diphenylamines-phosphine of the present embodiment-oxazoline ligand (1b), R1It is selected as ethyl, R2It is selected as phenyl, structural formula are as follows:
The preparation method of above-mentioned diphenylamines-phosphine-oxazoline ligand is substantially the same manner as Example 1, the difference is that step Amido alcohol choosing (S) -2 amino butanol (D2) in S2.2 yield of intermediate E is 92%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.51 (br, 1H), 7.88 (dd, J=7.9,1.4Hz, 1H), 7.81 (dd, J=7.9,1.6Hz, 1H), 7.45 (dd, J=1.4Hz, 1H), 7.31-7.22 (m, 2H), 7.18 (dd, J=8.4,0.8Hz, 1H), 6.83-6.74 (m, 2H), 4.42 (dd, J=9.6,7.8Hz, 1H), 4.37-4.28 (m, 1H), 3.96 (dd, J=8.0, 7.8Hz, 1H), 1.81-1.71 (m, 1H), 1.71-1.60 (m, 1H), 1.06 (t, J=7.4Hz, 3H)；13C NMR: (125.8MHz,CDCl3)δ163.2,145.0,143.3,139.9,131.7,129.9,128.6,124.4,121.9,117.7, 113.8,111.4,94.0,70.7,68.2,28.9,10.5；HRMS Calcdfor[C17H17IN2O+H]+:393.0458； found:393.0455.
The yield of product 1b is 86%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.36 (br, 1H), 7.68 (dd, J=8.0,1.6Hz, 1H), 7.48 (dd, J=8.0,4.7Hz, 1H), 7.35-7.22 (m, 11H), 7.18-7.12 (m, 1H), 7.08-6.98 (m, 2H), 6.88-6.82 (m, 1H), 6.71-6.65 (m, 1H), 4.25 (dd, J=8.6,7.4Hz, 1H), 3.96-3.83 (m, 1H), 1.40-1.22 (m, 2H), 0.82 (t, J=7.6Hz, 3H)；13C NMR:(125.8MHz,CDCl3) δ 163.1,146.1,145.0 (d, J= 21.8Hz), 137.1 (d, J=11.6Hz), 134.2,134.0,133.9,133.84,133.77,132.4 (d, J= 11.6Hz),131.5,129.6,129.4,128.5,128.4,128.3,124.1,116.8,113.6,110.7,70.3, 67.8,28.4,9.9；31P NMR(CDCl3,161MHz)δ-16.4；HRMS Calcd for[C29H27N2OP+H]+: 451.1934；found:451.1946.
Embodiment 3
In the diphenylamines-phosphine of the present embodiment-oxazoline ligand (1c), R1It is selected as isopropyl, R2It is selected as phenyl, structural formula Are as follows:
The preparation method of above-mentioned diphenylamines-phosphine-oxazoline ligand is substantially the same manner as Example 1, the difference is that:
In step S2, solvent uses benzene, and catalyst selects aluminium chloride, and amido alcohol selects (S) -2 amino -3- methylpropanol (D3). The yield of intermediate E 3 is 87%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.46 (br, 1H), 7.88 (dd, J=8.0,1.4Hz, 1H), 7.81 (dd, J=8.0,1.6Hz, 1H), 7.45 (dd, J=8.0,1.2Hz, 1H), 7.31-7.21 (m, 2H), 7.17 (d, J=8.4Hz, 1H), 6.83-6.74 (m, 2H), 4.37 (dd, J=9.6,8.1Hz, 1H), 4.22-4.13 (m, 1H), 4.04 (dd, J=8.2, 8.0Hz, 1H), 1.90-1.79 (m, 1H), 1.07 (d, J=6.8Hz, 3H), 0.98 (d, J=6.8Hz, 3H)；13C NMR: (125.8MHz,CDCl3)δ163.2,145.1,143.3,139.9,131.7,129.9,128.6,124.5,122.2,117.7, 113.8,111.3,94.2,73.0,68.9,33.1,19.1,18.8；HRMS Calcd for[C18H19IN2O+H]+: 407.0615；found:407.0621.
The yield of pure products 1c is 87%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.43 (br, 1H), 7.68 (dd, J=8.0,1.4Hz, 1H), 7.46 (dd, J=8.0,4.6Hz, 1H), 7.35-7.20 (m, 11H), 7.16-7.09 (m, 1H), 7.05-6.97 (m, 2H), 6.89-6.83 (m,1H),6.70-6.63(m,1H),4.25-4.15(m,1H),4.00-3.88(m,2H),1.62-1.49(m,1H),0.88 (d, J=6.6Hz, 3H), 0.78 (d, J=6.6Hz, 3H)；13C NMR:(125.8MHz,CDCl3)δ-16.4；HRMS Calcd for[C30H29N2OP+H]+:465.2090；found:465.2092.
Embodiment 4
In the diphenylamines-phosphine of the present embodiment-oxazoline ligand (1d), R1It is selected as tert-butyl, R2It is selected as phenyl, structural formula Are as follows:
Above-mentioned diphenylamines-phosphine-oxazoline ligand (1d) preparation method is substantially the same manner as Example 1, the difference is that: In step S2, solvent uses acetonitrile, and amido alcohol selects (S) -2 amino -3,3- dimethyl propyl alcohol (D4).The yield of intermediate E is 90%, testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.40 (br, 1H), 7.89 (dd, J=7.9,1.4Hz, 1H), 7.81 (dd, J=7.9,1.6Hz, 1H), 7.45 (dd, J=8.1,1.3Hz, 1H), 7.32-7.21 (m, 2H), 7.14 (d, J=8.4Hz, 1H),6.83-6.75(m,2H),4.34-4.25(m,1H),4.19-4.10(m,2H),0.99(s,9H)；13C NMR: (125.8MHz,CDCl3)δ163.2,145.3,143.3,139.9,131.7,130.0,128.6,124.7,122.6,117.7, 113.8,111.2,94.5,76.5,67.1,34.0,26.2；HRMS Calcd for[C19H21IN2O+H]+:421.0771； found:421.0778.
The yield of pure products 1d is 85%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.47 (br, 1H), 7.67 (dd, J=8.0,1.6Hz, 1H), 7.43 (dd, J=8.0,4.8Hz, 1H), 7.35-7.20 (m, 11H), 7.14-7.07 (m, 1H), 7.06-6.99 (m, 1H), 6.91 (d, J= 8.6Hz, 1H), 6.90-6.84 (m, 1H), 6.68-6.62 (m, 1H), 4.20 (dd, J=9.8,8.2Hz, 1H), 4.07 (dd, J =8.2,8.0Hz, 1H), 4.00 (dd, J=9.8,8.2Hz, 1H), 0.87 (s, 9H)；13C NMR:(125.8MHz,CDCl3)δ 163.2,146.5,145.2 (d, J=22.2Hz), 137.1 (d=12.0Hz), 137.0 (d=11.6Hz), 134.3,133.9, (133.83,133.78,133.68,133.3 d=11.4Hz), 131.4,129.6,129.5,128.5,128.41,128.39, 128.34,128.28,124.5,124.4,116.6,113.4,110.5,76.4,66.9,33.9,26.0；31P NMR(CDCl3, 161MHz)δ-16.9；HRMSCalcd for[C31H31N2OP+H]+:479.2247；found:479.2246.
Embodiment 5
In the diphenylamines-phosphine of the present embodiment-oxazoline ligand (1e), R1It is selected as phenyl, R2It is selected as phenyl, structural formula are as follows:
The preparation method of above-mentioned diphenylamines-phosphine-oxazoline ligand is substantially the same manner as Example 1, the difference is that: step In S2, solvent uses chlorobenzene, and amido alcohol selects (S) -2 amino -2- phenyl propanol (D5).The yield of intermediate E 5 is 86%.It is intermediate The testing result of body E is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.50 (br, 1H), 7.89 (dd, J=8.0,1.4Hz, 1H), 7.85 (dd, J=8.0,1.2Hz, 1H), 7.46 (dd, J=8.0,1.2Hz, 1H), 7.41-7.32 (m, 4H), 7.32-7.24 (m, 3H), 7.14 (d, J=8.6Hz, 1H), 6.86-6.74 (m, 2H), 5.53 (dd, J=10.0,8.4Hz, 1H), 4.75 (dd, J= 10.0,8.2Hz, 1H), 4.20 (dd, J=8.4,8.2Hz, 1H)；13C NMR:(125.8MHz,CDCl3)δ164.7,145.5, 143.1,142.2,139.9,132.1,130.2,128.6,128.6,127.5,126.7,124.9,122.9,117.6, 113.6,110.6,94.9,73.1,70.0；HRMS Calcd for[C21H17IN2O+H]+:441.0458；found: 441.0460.
The yield of pure products 1e is 90%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.29 (br, 1H), 7.76 (dd, J=8.0,1.6Hz, 1H), 7.49 (dd, J=8.0,4.6Hz, 1H), 7.36-7.11 (m, 17H), 7.08 (d, J=8.6Hz, 1H), 7.04-6.98 (m, 1H), 6.87- 6.80 (m, 1H), 6.74-6.66 (m, 1H), 5.07 (dd, J=10.0,8.0Hz, 1H), 4.56 (dd, J=10.0,8.2Hz, 1H), 4.00 (dd, J=8.0,8.0Hz, 1H)；13C NMR:(125.8MHz,CDCl3) δ 164.7,146.5,144.7 (d, J= 21.6Hz), 142.6,136.7 (d, J=11.2Hz), 136.6 (d, J=11.8Hz), 134.1,134.05,133.9,133.7, 133.6,132.8 (d, J=11.2Hz), 131.9,129.8,129.4,128.45,128.41,128.32,128.31, (128.27,127.1,126.5,124.4 d, J=2.4Hz), 124.3,116.9,113.8,110.2,73.0,69.7；31P NMR (CDCl3,161MHz)δ-16.6；HRMSCalcd for[C33H27N2OP+H]+:499.1934；found:499.1930.
Embodiment 6
In the diphenylamines-phosphine of the present embodiment-oxazoline ligand (1f), R1It is selected as benzyl, R2It is selected as phenyl, structural formula are as follows:
Above-mentioned diphenylamines-phosphine-oxazoline ligand (1f) preparation method is substantially the same manner as Example 1, the difference is that: In step S2, solvent uses dimethylbenzene, and catalyst selects aluminium chloride, and amido alcohol selects 2- amino -3- phenyl propanol (D6).Intermediate E 6 Yield be 87%, testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.43 (br, 1H), 7.88 (d, J=7.8Hz, 1H), 7.79 (d, J= 7.8Hz, 1H), 7.45 (d, J=8.2Hz, 1H), 7.31-7.19 (m, 8H), 7.16 (d, J=8.6Hz, 1H), 6.84-6.74 (m, 2H), 4.75-4.65 (m, 1H), 4.33 (dd, J=8.6,9.0Hz, 1H), 4.08 (dd, J=8.0,7.8Hz, 1H), 3.21 (dd, J=13.6,6.2Hz, 1H), 2.83 (dd, J=13.6,8.0Hz, 1H)；13CNMR:(125.8MHz,CDCl3)δ163.7, 145.1,143.3,139.9,138.0,131.9,130.0,129.3,128.6,128.5,126.4,124.6,122.0, 117.8,114.0,111.2,94.3,70.4,67.9,41.9；HRMSCalcd for[C22H19IN2O+H]+:455.0615； found:455.0616.
The yield of pure products 1f is 91%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.29 (br, 1H), 7.66 (dd, J=8.0,1.6Hz, 1H), 7.50 (dd, J=8.0,4.8Hz, 1H), 7.39-7.23 (m, 13H), 7.23-7.15 (m, 2H), 7.15-7.10 (m, 2H), 7.10-7.01 (m, 2H), 6.89-6.83 (m, 1H), 6.72-6.65 (m, 1H), 4.26-4.16 (m, 1H), 4.07 (dd, J=8.8,8.6Hz, 1H), 3.92 (dd, J=8.2,6.8Hz, 1H), 2.69 (dd, J=13.8,4.2Hz, 1H), 2.35 (dd, J=13.8,9.6Hz, 1H)；13C NMR:(125.8MHz,CDCl3) δ 163.7,146.3,144.9 (d, J=21.8Hz), 138.0,137.2 (d, J= 5.4Hz), 137.1 (d, J=6.0Hz), 134.2,134.1,134.0,133.9,133.8,132.4 (d, J=11.0Hz), 131.7,129.6,129.5,129.2,128.6,128.5,128.42,128.41,126.3,124.3,116.9,113.8, 110.5,69.7,67.5,41.2；31P NMR(CDCl3,161MHz)δ-16.5；；HRMS Calcd for[C34H29N2OP+H]+: 513.2090；found:513.2098.
Embodiment 7
In the diphenylamines-phosphine of the present embodiment-oxazoline ligand (1g), structural formula are as follows:
Above-mentioned diphenylamines-phosphine-oxazoline ligand (1g) preparation method is substantially the same manner as Example 1, the difference is that:
In step S2, solvent uses dimethylbenzene, and catalyst selects aluminium chloride, catalyst, 2- (2- iodophenyl) amido cyanophenyl (C) Molar ratio with amido alcohol (D7) is 1:10:75.The yield of intermediate E 7 is 87%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.49 (br, 1H), 7.88 (dd, J=8.0,1.6Hz, 1H), 7.80 (dd, J=7.8,1.6Hz, 1H), 7.62-7.55 (m, 1H), 7.41 (dd, J=8.0,1.2Hz, 1H), 7.30-7.14 (m, 6H), 6.80-6.71 (m, 2H), 5.83 (d, J=7.8Hz, 1H), 5.43-5.36 (m, 1H), 3.51 (dd, J=18.0,6.8Hz, 1H), 3.38 (dd, J=18.0,1.2Hz, 1H)；13C NMR:(125.8MHz,CDCl3)δ163.7,144.9,143.2, 142.0,139.9,139.6,131.8,130.1,128.6,128.4,127.3,125.9,125.2,124.3,121.6, 117.8,113.9,111.4,93.8,81.5,76.95,39.7；HRMS Calcd for[C22H17IN2O+H]+:453.0458； found:453.0463.
The yield of pure products 1g is 91%, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3) δ 10.35 (br, 1H), 7.66 (dd, J=8.0,1.6Hz, 1H), 7.43 (dd, J=8.0,4.6Hz, 1H), 7.37-7.25 (m, 11H), 7.22-7.08 (m, 4H), 7.06-6.97 (m, 3H), 6.92-6.84 (m, 1H), 6.67-6.60 (m, 1H), 5.40 (d, J=7.7Hz, 1H), 5.26-5.21 (m, 1H), 3.41 (dd, J=18.0, 6.4Hz, 1H), 3.30 (d, J=18.0Hz, 1H)；13C NMR:(125.8MHz,CDCl3)δ163.8,146.0,144.8(d,J =21.8Hz), 142.1,139.5,137.2 (d, J=12.2Hz), 137.1 (d, J=11.0Hz), 134.2,134.1, 134.0,133.94,133.87,132.3 (d, J=11.8Hz), 131.5,129.7,129.3,128.6,128.5,128.4, 128.3,128.2,127.1,126.0,125.0,124.2,124.1,116.7,113.4,110.5,81.4,76.6,39.5；31P NMR(CDCl3,161MHz)δ-16.8；HRMS Calcd for[C34H27N2OP+H]+:511.1934；found:511.1946.
Embodiment 8
The present embodiment is synthesisAnother method, include the following steps:
Step 1: sequentially adding CuI (0.5mmol), PPh under nitrogen atmosphere, in reaction flask2PH (10.5mmol), dimethyl Ethylenediamine (3.5mmol) and toluene (20mL) are stirred at room temperature and adjacent Iodoaniline (A) (10mmol) and Cs are added after ten minutes2CO3 (20mmol) is warming up to back flow reaction 10 hours.It is down to room temperature after reaction, silica gel filters, and filtrate decompression rotary evaporation removes Solvent is removed, column chromatography for separation obtains intermediate F (yield 96%).
Intermediate F is white solid, and testing result is as follows:
1H NMR:(399.9MHz,CDCl3)δ7.40-7.28(m,10H),7.21-7.14(m,1H),6.79-6.73(m, 1H),6.71-6.65(m,2H),4.14(br,2H)；13C NMR:(125.8MHz,CDCl3) δ 151.6 (d, J=19.8Hz), 136.3 (d, J=9.2Hz), 135.1,133.8 (d, J=8.2Hz), 134.4 (d, J=8.0Hz), 131.3,129.0,119.6 (d, J=8.0Hz), 119.0,115.7 (d, J=14.2Hz)；31P NMR(CDCl3,161MHz)δ-19.65.
Step 2: room temperature, under nitrogen atmosphere, sequentially added in reaction flask potassium tert-butoxide (20mmol, 2equiv.), it is dry DMSO (20mL) and intermediate F (10mmol, 1equiv.), obtains a dark solution.It is stirred at room temperature after ten minutes, reaction flask turns It moves in -10 DEG C of ice makers and stirs, o Flurobenzonitrile (12mmol, 1.2equiv.) is added under nitrogen atmosphere.Reaction flask turns after completion of dropwise addition It moves to and reaction 1-2 hours is stirred at room temperature.
100mL saturated salt solution and 50mL ethyl acetate, liquid separation are added after reaction；Water phase is extracted with ethyl acetate again Twice, merge organic phase, it is dry that anhydrous sodium sulfate is added.Filtering, filtrate decompression rotary evaporation remove solvent, and column chromatography for separation obtains To intermediate G (yield 88%).
Intermediate G is oily thick liquid, testing result are as follows:
1H NMR:(399.9MHz,CDCl3) δ 7.57 (dd, J=7.8,1.6Hz, 1H), 7.52-7.45 (m, 1H), 7.42- 7.29 (m, 14H), 7.27-7.21 (m, 1H), 7.15 (d, J=8.4Hz, 1H), 7.13-7.05 (m, 2H), 6.97-6.90 (m, 2H),6.79-6.73(m,1H),6.42(br,1H).
Step 3: sequentially adding intermediate G (10mmol) under air atmosphere, in reaction flask, (12mmol, R1 are first to amido alcohol Base), toluene (10mL), ZnCl2(1mmol) is warming up to the 5 day time of back flow reaction.It is down to room temperature after reaction, silica gel is taken out Filter, filtrate decompression rotary evaporation remove solvent, and column chromatography for separation obtains pure products 1a, and (yield 90%, product nuclear magnetic data are shown in Embodiment 1).
Embodiment 9
The present embodiment is synthesisAnother method, as different from Example 8, including walk as follows It is rapid:
In the first step, cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:7:40: 20:20, intermediate F yield are 95%, testing result such as embodiment 8.
In second step, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are 1:10:5；Reaction flask after completion of dropwise addition Be transferred to be stirred at room temperature the reaction time be 1.2 hours, obtained Intermediates Intermediate G, yield 87%, testing result as implement Example 8.
In third step, solvent is chlorobenzene；Catalyst is trifluoromethayl sulfonic acid zinc, catalyst, intermediate G and amido alcohol (R1 For ethyl) molar ratio be 1:10:10.
The yield of pure products 1b is 78%, and product nuclear magnetic data is shown in embodiment 2.
Embodiment 10
The present embodiment is synthesisAnother method, as different from Example 8, including walk as follows It is rapid:
In the first step, cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:7:100: 100:100, intermediate F yield are 92%, testing result such as embodiment 8.
In second step, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are 2:5:7；Reaction flask turns after completion of dropwise addition Move to be stirred at room temperature the reaction time be 2 hours, obtained Intermediates Intermediate G, yield 87%, testing result such as embodiment 8.
In third step, solvent is dimethylbenzene；Catalyst is aluminium chloride, and (R1 is isopropyl for catalyst, intermediate G and amido alcohol Base) molar ratio be 1:10:95.
The yield of pure products 1c is 87%, and product nuclear magnetic data is shown in embodiment 3.
Embodiment 11
The present embodiment is synthesisAnother synthetic method, as different from Example 8, including such as Lower step:
In the first step, cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:7:45: 25:45, intermediate F yield are 95%, testing result such as embodiment 8.
In second step, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are 1:1.2:2, reaction flask after completion of dropwise addition Be transferred to be stirred at room temperature the reaction time be 2 hours, obtained Intermediates Intermediate G, yield 89%, testing result such as embodiment 8。
In third step, solvent is chlorobenzene；Catalyst is trifluoromethayl sulfonic acid zinc, catalyst, intermediate H and amido alcohol (R1 For tert-butyl) molar ratio be 1:(1~10000): (1~10000)；Preferably 1:(10~100): (10~100).
The yield of pure products 1d is 85%, and product nuclear magnetic data is shown in embodiment 4.
Embodiment 12
The present embodiment is synthesisAnother method, as different from Example 8, including walk as follows It is rapid:
In the first step, cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:7:40: 20:45, intermediate F yield are 96%, testing result such as embodiment 8.
In second step, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are 2:1:10；Reaction flask after completion of dropwise addition Be transferred to be stirred at room temperature the reaction time be 1.5 hours, obtained Intermediates Intermediate G, yield 87%, testing result as implement Example 8.
In third step, solvent is ether；Catalyst is silver trifluoromethanesulfonate；(R1 is for catalyst, intermediate G and amido alcohol Ph molar ratio) is 1:50:75.
The yield of pure products 1e is 78-90%, and product nuclear magnetic data is shown in embodiment 5.
Embodiment 13
The present embodiment is synthesisAnother method, as different from Example 8, including walk as follows It is rapid:
In the first step, cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:7:100: 25:45, intermediate F yield are 92%, testing result such as embodiment 8.
In second step, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are 1:1.2:2, reaction flask after completion of dropwise addition Be transferred to be stirred at room temperature the reaction time be 2 hours, obtained Intermediates Intermediate G, yield 87%, testing result such as embodiment 8。
In third step, solvent is carbon tetrachloride；Catalyst is copper trifluoromethanesulfcomposite；Catalyst, intermediate G and amido alcohol The molar ratio of (R1 Bn) is 1:15:10.
The yield of pure products 1f is 87%, and product nuclear magnetic data is shown in embodiment 6.
Embodiment 14
The present embodiment is synthesisAnother method, as different from Example 8, including walk as follows It is rapid:
In the first step, cuprous iodide, dimethyl-ethylenediamine, Cs2CO3, two the molar ratio of phosphine hydrogen and A is replaced to be 1:7:55: 20:35, intermediate F yield are 94%, testing result such as embodiment 8.
In second step, the molar ratio of intermediate F, o Flurobenzonitrile and potassium tert-butoxide are 1:1.2:2, reaction flask after completion of dropwise addition Be transferred to be stirred at room temperature the reaction time be 1 hour, obtained Intermediates Intermediate G, yield 88%, testing result such as embodiment 8。
In third step, solvent is chlorobenzene；Catalyst is zinc chloride, and the molar ratio of catalyst, intermediate G and amido alcohol is 1: 10:25.
The yield of pure products 1g is 89%, and product nuclear magnetic data is shown in embodiment 7.
Embodiment 15
Diphenylamines-phosphine-oxazoline-iron complex synthesis
Room temperature under nitrogen atmosphere, sequentially adds the product 1 (1mmol) of embodiment 1 in reaction flask, n-hexane (n-hexane, 5mL) and frerrous chloride, reaction solution gradually become brown-green, filter after being stirred to react 5 hours, and filter cake is washed (every three times with n-hexane Secondary 5mL), filter cake is collected, oil pump is drained to obtain brown-green pulverulent solids.
Brown-green pulverulent solids, yield 86%.Anal.Calcd for C28H25Cl2FeN2OP:C,59.71；H, 4.47；N,4.97；Found:C,59.19；H,4.96；N,4.33.
It is changed to the product 1 of embodiment 2-7, using the preparation method of embodiment 15, obtains a series of complexs.
Brown-green pulverulent solids, yield 89%.Anal.Calcd for C29H27Cl2FeN2OP:C,60.34；H, 4.71；N,4.85；Found:C,59.99；H,4.83；N,4.63.
Brown-green pulverulent solids, yield 92%.Anal.Calcd for C30H29Cl2FeN2OP:C,60.94；H, 4.94；N,4.74；Found:C,60.91；H,4.76；N,4.99.
Brown-green pulverulent solids, yield 93%.Anal.Calcd for C31H31Cl2FeN2OP:C,61.51；H, 5.16；N,4.63；Found:C,61.44；H,4.86；N,4.52.
Brown-green pulverulent solids, yield 90%.Anal.Calcd for C33H27Cl2FeN2OP:C,63.39；H, 4.35；N,4.48；Found:C,63.32；H,4.56；N,4.38.
Brown-green pulverulent solids, yield 96%.Anal.Calcd for C34H29Cl2FeN2OP:C,63.87；H, 4.57；N,4.38；Found:C,63.62；H,4.69；N,4.22.
Brown-green pulverulent solids, yield 86%.Anal.Calcd for C34H27Cl2FeN2OP:C,64.08；H, 4.27；N,4.40；Found:C,64.00；H,4.39；N,4.12.
Embodiment 16
Diphenylamines-phosphine-oxazoline-cobalt complex synthesis
Room temperature under nitrogen atmosphere, sequentially adds the product 1 (1mmol) that embodiment 8 obtains, n-hexane (n- in reaction flask Hexane, 5mL) and cobalt chloride, reaction solution gradually deepen green, filtered after being stirred to react 5 hours, filter cake washs three with n-hexane Secondary (each 5mL), collects filter cake, and oil pump is drained to obtain dark green powder shape solid.
Dark green powder shape solid, yield 91%.Anal.Calcd for C28H25Cl2CoN2OP:C,59.38；H, 4.45；N,4.95；Found:C,59.09；H,4.56；N,4.23.
The product 1 that replacement embodiment 9-14 is obtained obtains a series of complexs using the method for embodiment 16.
Dark green powder shape solid, yield 90%.Anal.Calcd for C29H27Cl2CoN2OP:C,60.02；H, 4.69；N,4.83；Found:C,59.78；H,4.70；N,4.66.
Dark green powder shape solid, yield 96%.Anal.Calcd for C30H29Cl2CoN2OP:C,60.62；H, 4.92；N,4.71；Found:C,60.19；H,4.77；N,4.55.
Dark green powder shape solid, yield 94%.Anal.Calcd for C31H31Cl2CoN2OP:C,61.20；H, 5.14；N,4.60；Found:C,61.04；H,4.88；N,4.32.
Dark green powder shape solid, yield 89%.Anal.Calcd for C33H27Cl2CoN2OP:C,63.08；H, 4.33；N,4.46；Found:C,63.01；H,4.55；N,4.19.
Dark green powder shape solid, yield 95%.Anal.Calcd for C34H29Cl2CoN2OP:C,63.57；H, 4.55；N,4.36；Found:C,63.19；H,4.66；N,4.01.
Dark green powder shape solid, yield 90%.Anal.Calcd for C34H27Cl2CoN2OP:C,63.77；H, 4.25；N,4.37；Found:C,63.26；H,4.22；N,4.06.
Embodiment 17
Utilize the asymmetric hydrogenation for the iron complex catalytic iron catalyzed alkene that embodiment 15 obtains
At room temperature, (chirality) diphenylamines-phosphine-oxazoline-FeCl is added in a dry reaction tube2Complex (0.005mmol), alkene (0.5mmol), toluene (1mL), test tube connect 1 hydrogen balloon after vacuumizing, are injected into boron triethyl Sodium hydride (0.015mmol), column chromatography for separation obtains a series of product after being then stirred at room temperature 1 hour.
Oily liquids, > 99% yield, [α]20 D=-23.0 (c 0.83, CHCl3), 96.4%ee；1H NMR: (400.1MHz,CDCl3)δ7.14-7.03(m,4H),2.65-2.49(m,1H),2.31(s,3H),1.64-1.52(m,2H), 1.22 (d, J=6.8Hz, 3H), 0.82 (t, J=7.2Hz, 3H)
Oily liquids, > 99% yield, [α]20 D=-26.0, (c 0.96, CHCl3), 95.8%ee；1H NMR: (400.1MHz,CDCl3) δ 7.09 (d, J=8.4Hz, 2H), 6.83 (d, J=8.4Hz, 2H), 3.78 (s, 3H), 2.60-2.48 (m, 1H), 1.61-1.49 (m, 2H), 1.21 (d, J=7.0Hz, 3H), 0.81 (t, J=7.4Hz, 3H)
Oily liquids, > 99% yield, [α]20 D=-24.2 (c 0.66, CHCl3), 94.4%ee；1H NMR: (400.1MHz,CDCl3)δ7.32-7.23(m,2H),7.22-7.13(m,3H),2.72-2.59(m,1H),1.62-1.48(m, 2H), 1.34-1.08 (m, 7H), 0.85 (t, J=6.8Hz, 3H)
Oily liquids, > 99% yield, [α]20 D=-20.4 (c 1.01, CHCl3)；96.0%ee；1H NMR: (400.1MHz,CDCl3)δ7.32-7.22(m,2H),7.22-7.11(m,3H),2.84-2.70(m,1H),1.58-1.31(m, 3H), 1.20 (d, J=7.0Hz, 3H), 0.87 (d, J=6.0Hz, 3H), 0.84 (d, J=6.0Hz, 3H)
Oily liquids, > 99% yield, [α]20 D=-14.0 (c 0.88, CHCl3)；99.2%ee；1H NMR: (400.1MHz,CDCl3)δ7.17-7.07(m,2H),7.02-6.91(m,2H),3.64(s,3H),2.75-2.60(m,1H), 2.26 (t, J=6.2Hz, 2H), 1.65-1.41 (m, 4H), 1.22 (d, J=6.8Hz, 3H)；13C NMR:(100.6MHz, CDCl3) δ 174.0,161.2 (d, J=241.4Hz), 142.7 (d, J=3Hz), 128.2 (d, J=8Hz), 115.0 (d, J= 20.4Hz),51.4,39.1,37.8,34.0,23.0,22.4；19F NMR:(376MHz,CDCl3)δ-117.66；HRMS(EI) calculated for[C13H17FO2]+requires m/z224.1213,foundm/z 224.1208.
Embodiment 18
The hydrogenation of frerrous chloride catalyzed alkene
At room temperature, frerrous chloride (FeCl is added in a dry reaction tube2) (0.005mmol), alkene (0.5mmol), toluene (1mL), test tube connect 1 hydrogen balloon after vacuumizing, are injected into sodium triethylborohydride (0.015mmol), column chromatography for separation obtains product after being then stirred at room temperature 1 hour.
Oily liquids, 12% yield, [α]20 D=0, (c 0.96, CHCl3), 0%ee；
Embodiment 19
Utilize the asymmetric hydrogenation for the cobalt complex catalysis ketone that embodiment 16 obtains
At room temperature, (chirality) diphenylamines-phosphine-oxazoline-CoCl is added in a dry reaction tube2Complex (0.005mmol), ketone (0.5mmol), potassium tert-butoxide (0.015mmol) and toluene (1mL), test tube connect 1 hydrogen after vacuumizing Balloon is injected into sodium triethylborohydride (0.015mmol), and column chromatography for separation is produced after being then stirred at room temperature 1 hour Object.
Oily liquids, 99% yield, [α]20 D=+59.5 (c 1.0, CHCl3)；98.1%ee；1H NMR(CDCl3, 400MHz):δ7.27-7.40(m,4H),7.24-7.30(m,1H),4.84-4.93(m,1H),1.93(br,1H),1.49(d,J =6.2Hz, 3H)
Oily liquids, 99% yield, [α]20 D=+55.4 (c 1.01, CHCl3)；98.7%ee；1H NMR(CDCl3, 400MHz): δ 7.27 (d, J=7.8Hz, 2H), 7.16 (d, J=7.8Hz, 2H), 4.82-4.92 (m, 1H), 2.34 (s, 3H), 1.79 (br, 1H), 1.48 (d, J=6.4Hz, 3H)
Oily liquids, 99% yield, [α]20 D=+16.5 (c 1.1, CHCl3)；95.5%ee；1H NMR(CDCl3, 400MHz): δ 7.30 (d, J=7.8Hz, 2H), 6.88 (d, J=7.8Hz, 2H), 4.82-4.91 (m, 1H), 3.81 (s, 3H), 1.73 (br, 1H), 1.48 (d, J=6.2Hz, 3H)
Oily liquids, 97% yield, [α]20 D=+38.5 (c 1.03, CHCl3)；97.6%ee；1H NMR(CDCl3, 400MHz): δ 7.27 (d, J=7.6Hz, 2H), 7.12 (d, J=7.0Hz, 2H), 4.80-4.90 (m, 1H), 2.46 (d, J= 6.8Hz,2H),1.78-1.97(m,2H),1.44-1.53(m,3H),0.85-0.96(m,6H).
Oily liquids, 99% yield, [α]20 D=+45.8 (c 0.97, CHCl3)；96.7%ee；1H NMR(CDCl3, 400MHz): δ 7.30-7.41 (m, 2H), 7.03 (t, J=8.6Hz, 2H), 4.81-4.92 (m, 1H), 1.95 (br, 1H), 1.47 (d, J=6.4Hz, 3H)
Oily liquids, 97% yield, [α]20 D=+44.2 (c 0.93, CHCl3)；96.1%ee；1H NMR(CDCl3, 400MHz): δ 7.23-7.34 (m, 4H), 4.79-4.87 (m, 1H), 2.30 (br, 1H), 1.44 (d, J=6.4Hz, 3H)
Oily liquids, 97% yield, [α]20 D=+35.7 (c 0.98, CHCl3)；96.0%ee；1H NMR(CDCl3, 400MHz): δ 7.47 (d, J=8.0Hz, 2H), 7.25 (d, J=8.0Hz, 2H), 4.82-4.92 (m, 1H), 1.84 (br, 1H), 1.47 (d, J=6.4Hz, 3H)
Oily liquids, 99% yield, [α]20 D=+24.8 (c 0.98, CHCl3)；96.0%ee；1H NMR(CDCl3, 400MHz):δ7.67-7.77(m,3H),7.43-7.50(m,1H),7.09-7.17(m,2H),4.98-5.06(m,1H),3.91 (s, 3H), 1.98 (br, 1H), 1.56 (d, J=6.2Hz, 3H)
Oily liquids, 95% yield, [α]20 D=-32.2 (c 1.15, CHCl3)；99.8%ee；1H NMR(CDCl3, 400MHz):δ7.38-7.46(m,1H),7.15-7.23(m,2H),7.06-7.14(m,1H),4.77(s,1H),2.66-2.88 (m,2H),1.68-2.04(m,5H).
Oily liquids, 99% yield, [α]20 D=+10.0 (c 1.14, CHCl3), 85.0%ee；1H NMR(CDCl3, 400MHz):δ3.50-3.59(m,1H),1.62-1.89(m,5H),1.38(br,1H),0.90-1.32(m,9H).
White solid, 92% yield, [α]20 D=+5.4 (c 0.94, CHCl3), 86.0%ee；1H NMR(CDCl3, 400MHz): δ 7.44 (d, J=7.0Hz, 1H), 7.00-7.30 (m, 8H), 5.85 (s, 1H), 2.53 (br, 1H), 2.16 (s, 3H).
Embodiment 20
The asymmetric hydrogenation of cobalt chloride catalysis ketone
At room temperature, cobalt chloride (CoCl is added in a dry reaction tube2) (0.005mmol), ketone (0.5mmol), Toluene (1mL), test tube connect 1 hydrogen balloon after vacuumizing, sodium triethylborohydride (0.015mmol) are injected into, then in room Temperature lower stirring 1 hour.Product is not found through gas phase-Mass Spectrometer Method after reaction.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each Kind change, modification and/or variation, all these equivalent forms equally fall within guarantor defined by the application the appended claims Within the scope of shield.

Claims (10)

1. diphenylamines-phosphine-oxazoline ligand, it is characterised in that: for compound described in formula (1)
It or is the enantiomer or raceme of formula (1) described compound；
Wherein, R1And R2It is each independently C1~C10Alkyl, benzyl, phenyl or substituted phenyl (substituent group C1~C6Hydrocarbon One of base, oxyl and halohydrocarbyl, substituent group quantity are 1-5) and heteroaryl.
2. diphenylamines-phosphine-oxazoline ligand as described in claim 1, it is characterised in that: R1Preferably methyl, ethyl, positive third One of base, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl or benzyl.
3. diphenylamines-phosphine-oxazoline ligand as claimed in claim 2, it is characterised in that: R2Preferably cyclohexyl or phenyl.
4. synthesizing diphenylamines-phosphine-oxazoline ligand approach as described in any one of claims 1-3, it is characterised in that: including such as Lower step:
Dimethyl sulfoxide solvent, adjacent Iodoaniline and potassium tert-butoxide is added in S1 under room temperature, inert atmosphere, in reactor, stirring is very Zhong Hou, reactor, which is transferred at -10 DEG C, is added dropwise o Flurobenzonitrile, continues to separate after reacting at room temperature a period of time after completion of dropwise addition To intermediate 2- (2- iodophenyl) amido cyanophenyl (C)；
Solvent, intermediate C, amido alcohol, catalyst is added at room temperature in S2 in reactor, then raise temperature to reflux, reacts one section The isolated iodo- 2 '-oxazolines-diphenylamines (E) of intermediate 2- after time；
S3 under room temperature, inert atmosphere, is added cuprous iodide, phosphine hydrogen, dimethyl-ethylenediamine and toluene, is stirred at room temperature in reactor Intermediate E and Cs are added after ten minutes2CO3, isolated product 1 after being warming up to back flow reaction for a period of time, institute as of the present invention Diphenylamines-phosphine-oxazoline the ligand stated.
5. synthetic method as claimed in claim 4, it is characterised in that: solvent described in step S2 is organic solvent, is polarity Or nonpolar solvent, the organic solvent are benzene, toluene, chlorobenzene, dimethylbenzene, carbon tetrachloride, petroleum ether, tetrahydrofuran, two It is methylformamide, ether, methylene chloride, chloroform, hexamethylene, n-hexane, normal heptane, dioxane, any in acetonitrile It is a kind of.
6. synthetic method as claimed in claim 4, it is characterised in that: the step S2 reaction catalyst be selected from zinc chloride, One of trifluoromethayl sulfonic acid zinc, aluminium chloride, iron chloride, copper trifluoromethanesulfcomposite, silver trifluoromethanesulfonate.
7. synthesizing diphenylamines-phosphine-oxazoline ligand approach as described in any one of claims 1-3, it is characterised in that: including such as Lower step:
The first step is added cuprous iodide, two replaces phosphine hydrogen, dimethyl-ethylenediamine and first under room temperature, inert atmosphere, in reactor Benzene is stirred at room temperature and adjacent Iodoaniline (A) and Cs is added after ten minutes2CO3, be warming up to back flow reaction for a period of time after it is isolated in Mesosome 2- bis- replaces phosphino- aniline (F)；
Dimethyl sulfoxide, intermediate F and potassium tert-butoxide is added at room temperature in second step in reactor, stirring after ten minutes, is reacted Device, which is transferred at -10 DEG C, is added dropwise o Flurobenzonitrile, continues the isolated intermediate after reacting at room temperature a period of time after completion of dropwise addition 2- [2- (two replace phosphino-) phenyl] amido cyanophenyl (G)；
Step 3: solvent, intermediate G, amido alcohol, catalyst are added in reactor, then raises temperature to back under room temperature, air atmosphere Stream reacts isolated product 1 after a period of time, diphenylamines-phosphine-oxazoline ligand as of the present invention.
8. synthetic method as claimed in claim 7, it is characterised in that: intermediate F, o Flurobenzonitrile and tertiary fourth in second step reaction The molar ratio of potassium alcoholate is 1:1.2:2.
9. diphenylamines-phosphine-oxazoline metal complex, it is characterised in that: by compound 1 described in claim 1 and element week Transition metal salt in phase table is formed, and has the general formula as described in formula (2)
Wherein, M is one of transition-metal Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, Ir；
X is selected from halide (F, Cl, Br, I), pseudohalide (cyanide, cyanic acid, salt, isocyanates), carboxylic acid, sulfonic acid, phosphonic acids Anion (carbonate, formate, acetate, propionate, methane sulfonic acid root, trichloromethyl sulfonate radical, phenylbenzimidazole sulfonic acid root, toluene Sulfonate radical) in any one；
E is H or alkyl；
N1 is the number of X, is 0,1,2,3；
N2 is the number of E, is 0 or 1.
10. diphenylamines-phosphine-oxazoline metal complex purposes refers at least one diphenylamines-phosphine-evil using catalytic amount By being catalyzed reaction, to prepare optical selective organic as catalyst for oxazoline ligand or diphenylamines-phosphine-oxazoline metal complex Compound.
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CN113135814A (en) * 2021-04-28 2021-07-20 温州大学 Method for synthesizing chiral 1, 2-diol compound
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