CN112824423B - Chiral ferrocenylphosphine-indolylaminophosphine ligand and preparation method and application thereof - Google Patents
Chiral ferrocenylphosphine-indolylaminophosphine ligand and preparation method and application thereof Download PDFInfo
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- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
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Abstract
A chiral ferrocenylphosphine-indolylaminophosphine ligand and a preparation method thereof are disclosed, a chiral ferrocenylphosphine-indole intermediate is dissolved in ether, n-BuLi of the chiral ferrocenylphosphine-indole intermediate is 0.5-1 2 0.5-1 dropwise adding ClPPh 2 The ether solution is decompressed, concentrated and separated by column chromatography to obtain the target chiral ferrocenylphosphine-indolylaminophosphine ligand. The asymmetric hydrogenation reaction of the catalyst formed of the ligand of the present invention with Rh metal precursor to C = C double bond has the advantage of high catalyst activity, TON can be as high as 10,000, and enantioselectivity can be as high as 96% ee.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a chiral ferrocenylphosphine-indolylaminophosphine ligand and a preparation method thereof, and the invention also relates to a preparation method of the ligand and application of the ligand in rhodium-catalyzed asymmetric hydrogenation reaction of C = C bond.
Background
Catalytic asymmetric hydrogenation is one of the most widely used organic reactions in the synthesis of chiral drugs, pesticides, fragrances and the like, wherein the reasonable use of chiral ligands is the key to realizing the important reaction. Over the past decades, a series of highly efficient chiral bidentate phosphine-containing ligands have emerged to be used in a variety of asymmetric catalytic hydrogenation reactions, such as BINAP, duPhos et al (Tang, w.; zhang, x.chem. Rev.2003,103, 3029-3069). Among them, phosphine-aminophosphine ligands are receiving increasing attention because of their simple synthesis, stable properties, and easy stepwise regulation. The first highly efficient chiral phosphine-aminophosphine ligands were reported in 2002 by Boaz et al, which showed excellent activity and stereoselectivity in Rh-catalyzed asymmetric hydrogenation of α -dehydroamino acids, dimethyl itaconate and α -keto acids (Boaz, n.w.; debeham, s.d.; mackenzie, e.b.; large, s.e.org.lett.2002,4, 2421-2424). <xnotran> , - (Krabbe, S.W.; hatcher, M.A.; bowman, R.K.; mitchell, M.B.; mcClure, M.S.; johnson, J.S.Org.Lett.2013,15,4560-4563;Hu,J.; wang, D.Y.; zheng, Z.; hu, X.P.Chin.J.Chem.2012,30,2664-2668;Gross,T.; chou, S.; dyke, A.; dominguez, B.; groarke, M.; medlock, J.; ouellette, M.; reddy, J.P.; seger, A.; zook, S.; zanotti-Gerosa, A.Tetrahedron Lett.2012,53,1025-1028;Zhou,X.M.; huang, J.D.; luo, L.B.; zhang, C.L.; zheng, Z.; hu, X.P.Tetrahedron: asymmetry 2010,21,420-424;Qiu,M.; hu, X.P.; huang, J.D.; wang, D.Y.; deng, J.; yu, S.B.; duan, Z.C.; zheng, Z.Adv.Synth.Catal.2008,350,2683-2689;Deng,J.; hu, X.P.; huang, J.D.; yu, S.B.; wang, D.Y.; duan, Z.C.; zheng, Z.J.Org.Chem.2008,73,2015-2017;Chen,W.P.; mbafor, W.; roberts, S.M.; whittall, J.J.Am.Chem.Soc.2006,128,3922-3923). </xnotran> However, the aminophosphines in the chiral phosphine-aminophosphine ligands are all derived from free primary amines or secondary amines, and the construction of the aminophosphine structure based on nitrogen on the nitrogen heterocycle is not reported in the literature. During the development of chiral ferrocene-indole diphosphine ligands, we have unexpectedly found that when the molar amount of n-BuLi is less than that of the starting chiral ferrocene-indole intermediate, diarylphosphination occurs at the 1-position of indole rather than the 2-position, thus synthesizing a novel chiral ferrocenylphosphine-indolylaminophosphine ligand. The ligand has the characteristics of wide synthetic raw material source, simple and convenient preparation process, stable property and the like, and has wide application in asymmetric catalytic hydrogenation reaction.
Disclosure of Invention
The invention aims to provide a chiral ferrocenylphosphine-indolylaminophosphine ligand.
It is a further object of the present invention to provide a process for the preparation of the above ligands and their use in rhodium catalysed asymmetric hydrogenation of C = C bonds.
The chiral ferrocenylphosphine-indolylaminophosphine ligand has the structures shown in the following formulas I and II:
formula I and formula II are enantiomers of each other.
In the formula: r is H, alkyl, cycloalkyl, etc. C 1 ～C 40 The aliphatic group containing or not containing functional groups such as N, S, O, P and the like; benzyl radical or the like C 7 -C 60 A combination group of an aromatic group and an aliphatic group, wherein the combination group contains or does not contain functional groups such as N, S, O, P and the like; aryl and the like C 6 -C 60 Aromatic groups containing or not containing functional groups such as N, S, O, P and the like; r has a predominant structure of-CH 3 。
Ar 'and Ar' are C 6 -C 60 The aromatic groups containing or not containing functional groups such as N, S, O, P and the like, ar 'and Ar' can be the same groups or different groups, and the advantageous structure is phenyl.
The invention provides a method for preparing the ligand I or II, which mainly comprises the following steps:
dissolving the chiral ferrocenylphosphine-indole intermediate III (or IV) in diethyl ether, dropwise adding n-BuLi in hexane solution at room temperature according to the molar ratio of n-BuLi =1 to 0.5-1, wherein the molar ratio of the chiral ferrocenylphosphine-indole intermediate III (or IV) to n-BuLi is less than or equal to 1, and continuously stirring and reacting at room temperature for 0.5-12 hours after dropwise adding. Then chiral ferrocenylphosphine-indole intermediate III (or IV): clPAr 'in molar ratio at room temperature' 2 0.5-1 of ClPAr' 2 The solution is dripped into the ethyl ether solution, and the stirring reaction is continued for 0.5 to 12 hours at room temperature. Decompressing, concentrating, and separating by column chromatography to obtain the needed chiral ferrocenylphosphine-indolylaminophosphine ligand I or II.
The decompression concentration and the column chromatography separation are carried out without water.
The structural formula of the chiral ferrocenylphosphine-indole intermediate is as follows:
the synthetic route of the ligand is as follows:
the intermediates III and IV of the invention are enantiomers of each other, wherein R and Ar 'are equivalent groups with R and Ar' in the ligands I and II.
The dosage of n-BuLi and the treatment method after reaction are the key points for synthesizing the chiral ferrocenylphosphine-indolylaminophosphine ligand. Wherein the molar amount of n-BuLi cannot exceed that of the chiral ferrocenylphosphine-indole intermediate III (or IV), namely the molar amount of n-BuLi is less than 1. No water or aqueous reagent is added after the reaction. Excess n-BuLi and post-treatment will lead to the formation of a chiral ferrocenylphosphine ligand or the decomposition of a chiral ferrocenylphosphine-indolylaminophosphine ligand when exposed to water.
The chiral ferrocenylphosphine-indolylaminophosphine ligand provided by the invention has the characteristics of simple synthetic route, stable property and the like, and the metal Rh complex has extremely high catalytic activity and enantioselectivity on hydrogenation reaction of C = C bond. The chiral catalyst formed in situ by the chiral ligand and the metal precursor can be used for preparing various chiral products such as chiral acid, chiral amino acid and the like and chiral intermediates for synthesizing chiral pesticides, medicines and the like by an asymmetric catalytic hydrogenation method, and has important application value in the industries such as medicines, pesticides, spices, food additives and the like.
The invention provides a chiral ferrocenyl phosphine-indolylaminophosphine ligand I or II and a rhodium metal precursor [ Rh (COD) 2 ]BF 4 、[Rh(BND) 2 ]BF 4 The catalysts formed under in situ conditions are mainly used in the following classesC = asymmetric hydrogenation of C bond:
(1) Catalytic asymmetric hydrogenation of alpha-dehydroamino acid esters
(2) Catalytic asymmetric hydrogenation of beta-dehydroamino acid esters
(3) Catalytic asymmetric hydrogenation of alpha-enamides
(4) Catalytic asymmetric hydrogenation of alpha-enol esters
(5) Catalytic asymmetric hydrogenation of itaconates
The hydrogenation reaction of C = C bond catalyzed by metal complex formed by chiral ferrocenylphosphine-indolylaminophosphine ligand I or II and Rh metal precursor in situ is carried out under the conditions of 1-100atm and-20-200 ℃, the reaction time is 0.1-48 hours, the molar ratio of a reaction substrate to a central metal is 100-10,000, and the solvent can be protic alcohol solvent methanol, ethanol, isopropanol and the like, and can also be aprotic solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, ethyl acetate and the like. Metal complexes of chiral ferrocenylphosphine-indolylaminophosphine ligands I or II with Rh metal precursors formed in situ catalyze the C = C bond hydrogenation reaction to obtain enantioselectivities up to 96% ee, with high catalytic activity, TON up to 10,000.
The invention has the beneficial effects that:
the chiral ferrocene-indolylaminophosphine ligand has the characteristics of simple and easily obtained synthetic raw materials, simple steps, wide application and the like, and the catalyst formed by the chiral ferrocene-indolylaminophosphine ligand and the Rh metal precursor has the advantages of high catalyst activity, high corresponding selectivity, small catalyst dosage and the like in the asymmetric hydrogenation reaction of C = C double bonds.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is (R) prepared in example 1 c ,S p ) -nuclear magnetic resonance hydrogen spectrum of I-1;
FIG. 2 is (R) prepared in example 1 c ,S p ) -nuclear magnetic resonance carbon spectrum of I-1;
FIG. 3 is (R) prepared in example 1 c ,S p ) -nuclear magnetic resonance phosphorus spectra of I-1;
Detailed Description
The technical features of the present invention have been explained more fully in the summary of the invention, and the following examples are intended to further illustrate the invention and should not be construed as limiting the invention. The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples:
example 1:
under the condition of nitrogen, 2.6g (5 mmol) of ferrocenylphosphine-indole intermediate III-1 is dissolved in 30mL of anhydrous ether, n-BuLi (2.5 mol/L,1.8mL,4.5 mmol) is dropwise added at room temperature, the dropwise addition is finished after 10min, the stirring reaction is continued for 1 hour after the dropwise addition is finished, clPPh is dropwise added into the reaction liquid 2 And (5 mmol) of ether solution, dripping for 1 hour, continuously stirring at room temperature for reaction for 12 hours, removing the solvent, and performing column chromatography separation (petroleum ether/ethyl acetate, 10/1) on the residue to obtain 3.1g of chiral ferrocenylphosphine-indolylaminophosphine ligand I-1, as shown in figures 1, 2 and 3. [ alpha ] of] D 20 ＝+157.8(c,1.0,CHCl 3 ). 1 H NMR(400MHz,CDCl 3 )δ7.51(m,3H),7.42(d,J＝7.1Hz,1H),7.32(m,7H),7.25(m,2H),7.16(2,1H),6.97(m,4H),6.82(t,J＝7.1Hz,1H),6.64(s,1H),6.59(t,J＝7.0Hz,2H),6.45(t,J＝7.0Hz,2H),5.27(s,1H),4.67(s,1H),4.45(m,1H),4.28(s,1H),3.95(s,5H),3.78(s,1H),1.77(d,J＝7.0Hz,3H). 31 P NMR(162MHz,CDCl 3 )δ36.1,-22.9。
Example 2:
the amount of n-BuLi used in example 1 was reduced to 3.75mmol, as in example 2, giving 2.4g of chiral ferrocenylphosphine-indolylaminophosphine ligand I-1.
Example 3:
the starting material (R) in example 2 was added c ,S p ) -III-1 to (S) c ,R p ) 3.0g of chiral ferrocenylphosphine-indolylaminophosphine ligand II-1 were obtained as in example 2.
2. Catalytic asymmetric hydrogenation
Example 4:
under the protection of nitrogen, 2.0mg (0.005 mmol) of [ Rh (COD) 2 ]BF 4 (R) prepared as described above c ,S p ) -I-1 (0.0055 mmol) and toluene (1.5 mL) as a solvent were placed in a 10mL reactor, and after 30 minutes of reaction, a solution of the substrate methyl 2-acetylamino-3-phenylpropionate (0.5 mmol) and 1.5mL of toluene was added, and after 3 times of replacement with hydrogen, the reaction was terminated after maintaining the normal pressure for 12 hours, followed by concentration, water washing, drying and desolventization to obtain methyl (S) -2-acetylamino-3-phenylpropionate in a yield of 100% (based on methyl 2-acetylamino-3-phenylpropionate) and an enantiomeric excess of 93% ee.
Example 5:
under nitrogen protection, 2.0mg (0.005 mmol) [ Rh (COD) ] 2 ]BF 4 (R) prepared as described above c ,S p ) -I-1 (0.0055 mmol) and toluene (1.5 mL) as a solvent were placed in a 10mL reactor, reacted for 30 minutes, then added a solution of the substrate methyl 3-acetylamino-3-phenylpropionate (0.5 mmol) and 1.5mL of toluene, replaced with hydrogen for 3 times, reacted under normal pressure for 12 hours, then terminated, concentrated, washed with water, dried and desolventized to obtain methyl (S) -3-acetylamino-3-phenylpropionate in a yield of 100% (based on methyl 3-acetylamino-3-phenylpropionate) and an enantiomeric excess of 95% ee.
Example 6:
under nitrogen protection, 2.0mg (0.005 mmol) [ Rh (COD) ] 2 ]BF 4 (R) prepared as described above c ,S p ) -I-1 (0.0055 mmol) and toluene (1.5 mL) as a solvent were placed in a 10mL reactor, and after 30 minutes of reaction, the substrate, alpha-acetamido, was addedA solution of phenylstyrene (0.5 mmol) and 1.5mL of toluene was replaced with hydrogen for 3 times, and after maintaining the reaction at normal pressure for 12 hours, the reaction was terminated, followed by concentration, washing with water, and drying for desolventization, whereby (S) -N-acetyl-alpha-phenylethylamine was obtained in a yield of 100% (based on alpha-acetamidostyrene) and an enantiomeric excess of 96% ee.
Example 7:
under nitrogen protection, 2.0mg (0.005 mmol) [ Rh (COD) ] 2 ]BF 4 (R) prepared as described above c ,S p ) -I-1 (0.0055 mmol) and toluene (1.5 mL) as a solvent were placed in a 10mL reactor, and after 30 minutes of reaction, a solution of the substrate a-acetoxystyrene (0.5 mmol) and 1.5mL of toluene was added, and after 3 times of hydrogen substitution, the reaction was terminated after maintaining the atmospheric pressure for 12 hours, followed by concentration, water washing, drying and desolventization to obtain (S) - α -acetoxyethylbenzene in a yield of 100% (in terms of α -acetoxystyrene) with an enantiomeric excess of 94% ee.
Example 8:
under the protection of nitrogen, 2.0mg (0.005 mmol) of [ Rh (COD) 2 ]BF 4 (R) prepared as described above c ,S p ) Placing I-1 (0.0055 mmol) and toluene (1.5 mL) as solvent in a 10mL reactor, reacting for 30 minutes, adding a solution of dimethyl itaconate (0.5 mmol) as substrate and 1.5mL of toluene, replacing with hydrogen for 3 times, maintaining normal pressure for 12 hours, terminating the reaction, concentrating, washing with water, drying and desolventizing to obtain (R) -2-dimethyl methylsuccinate with enantiomeric excess of 96% ee.
Claims (8)
1. A chiral ferrocenylphosphine-indolylaminophosphine ligand is characterized in that: the structural formula is as follows:
wherein formula I and II are enantiomers of each other;
in the formula: r is C 1 ～C 40 An alkyl group within;
ar 'and Ar' are phenyl groups.
2. The chiral ferrocenylphosphine-indolylaminophosphine ligand as claimed in claim 1, which is characterized in that: r has a predominant structure of-CH 3 (ii) a Ar 'and Ar' have the predominant structures of phenyl.
3. A process for the preparation of a chiral ferrocenylphosphine-indolylaminophosphine ligand as claimed in any one of claims 1 to 2, which comprises: dissolving chiral ferrocenylphosphine-indole intermediate III or IV in diethyl ether, and dropwise adding n-BuLi hexane solution at room temperature, wherein the molar ratio of n-BuLi to the chiral ferrocenylphosphine-indole intermediate III or intermediate IV<1; then ClPAr 'is added dropwise at room temperature' 2 With ClPAr 'and chiral ferrocenylphosphine-indole intermediate III (or IV)' 2 And (2) the molar ratio is 1:0.5-1, and the target chiral ferrocenylphosphine-indolylaminophosphine ligand is obtained through decompression concentration and column chromatography separation.
4. A method of preparing a chiral ferrocenylphosphine-indolylaminophosphine ligand according to claim 3, which is characterized in that: the structural formula of the chiral ferrocenylphosphine-indole intermediate is as follows:
5. A method of preparing a chiral ferrocenylphosphine-indolylaminophosphine ligand according to claim 3, which comprises the steps of: the decompression concentration and column chromatographic separation are carried out without water.
6. Use of a chiral ferrocenylphosphine-indolylaminophosphine ligand according to any one of claims 1 to 2 in rhodium-catalysed asymmetric hydrogenation of C = C bonds with high catalyst activity, TON up to 10,000 and enantioselectivity up to 96% ee.
7. Use of a chiral ferrocenylphosphine-indolylaminophosphine ligand according to claim 6 in rhodium catalyzed asymmetric hydrogenation of C = C bond, wherein the rhodium catalyzed asymmetric hydrogenation of C = C bond is catalyzed asymmetric hydrogenation of the following classes of substrates:
(1) Catalytic asymmetric hydrogenation of beta-dehydroamino acid esters
(2) Catalytic asymmetric hydrogenation of alpha-enamides
(3) Catalytic asymmetric hydrogenation of itaconate esters.
8. Use of a chiral ferrocenylphosphine-indolylaminophosphine ligand according to claim 6 in rhodium catalysed asymmetric hydrogenation of C = C bond, characterized in that: the hydrogenation reaction of C = C bond catalyzed by metal complex formed by chiral ferrocenylphosphine-indolylaminophosphine ligand I or II and Rh metal precursor in situ is carried out under the conditions of 1-100atm, -20-200 ℃, the reaction time is 0.1-48 hours, the molar ratio of a reaction substrate to a central metal is 100-10,000, and the solvent can be protic alcohol solvent methanol, ethanol, isopropanol and the like, and can also be aprotic solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, ethyl acetate and the like.
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| CN101486737A (en) * | 2009-03-06 | 2009-07-22 | 北京理工大学 | Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction |
| CN105153229A (en) * | 2015-06-18 | 2015-12-16 | 武汉凯特立斯科技有限公司 | Chiral tridentate PNN ligand and application of same in asymmetric hydrogenation |
| CN105481909A (en) * | 2015-11-11 | 2016-04-13 | 武汉凯特立斯科技有限公司 | Chiral diphosphine ligand and application thereof to asymmetric hydrogenation and correlated reactions |
| CN105949248A (en) * | 2016-05-26 | 2016-09-21 | 河南省科学院化学研究所有限公司 | Synthesis method of Josiphos chiral ferrocenyl phosphine ligands |
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