CN111450880B - Sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst - Google Patents
Sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst Download PDFInfo
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- CN111450880B CN111450880B CN202010385032.3A CN202010385032A CN111450880B CN 111450880 B CN111450880 B CN 111450880B CN 202010385032 A CN202010385032 A CN 202010385032A CN 111450880 B CN111450880 B CN 111450880B
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Abstract
The invention relates to a chiral catalyst integrating a phosphine ligand and polyether functionalized ionic liquid, which integrates a transition metal complex of chiral diphosphine ligand BINAP and polyether functionalized ionic liquid by utilizing the characteristics of designability and easy functionalization of the ionic liquid to obtain a catalyst integrating the phosphine ligand and the ionic liquid.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a phosphine ligand and polyether functionalized ionic liquid integrated catalyst.
Background
In the past decades, homogeneous asymmetric catalytic hydrogenation has become one of the most efficient and atomic economic means for obtaining fine chemicals such as chiral drugs, pesticides and fragrances due to its high catalytic activity, good stereoselectivity and mild reaction conditions. However, the problem of difficult separation of chiral noble metal catalysts (mainly chiral phosphine ligand-metal complexes) from hydrogenation products has long limited their large-scale industrial application. Therefore, the development of a recyclable and recyclable chiral catalyst has been the focus of research in the field of homogeneous asymmetric hydrogenation.
In recent years, with the increasing importance of green chemistry and the demand for environmentally friendly solvents, green solvent ionic liquids have attracted great attention. Different from the traditional organic solvent, the ionic liquid has the advantages of extremely low saturated vapor pressure, high thermal and chemical stability, good solubility to the transition metal catalyst, designability of the structure and the like, so that the ionic liquid serving as the catalyst carrier becomes an effective means for separating, recovering and recycling the chiral catalyst. Although ionic liquids have been used successfully for separating chiral catalysts in asymmetric hydrogenation reactions, a problem of difficult blending has been revealed, i.e. in order to suppress the loss of catalyst, a large amount of solvent ionic liquids are usually used in catalytic reactions to sufficiently dissolve and immobilize chiral catalysts (up to 140-5000 times (mol/mol) of metal catalysts, which is equivalent to 15-2100% of substrates, mol%), which neither meets the requirements of green chemistry, nor results in the waste of resources. And the application of a large amount of solvent ionic liquid also makes the negative effect (such as poisoning the catalyst) of trace impurities which are difficult to remove in the ionic liquid on the metal catalyst more remarkable, so that the catalytic efficiency is reduced. Therefore, how to apply the ionic liquid environmentally friendly and economically to construct a high-efficiency ionic liquid asymmetric hydrogenation system is a problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to integrate a transition metal complex of chiral diphosphine ligand BINAP and polyether functionalized ionic liquid to obtain a class of catalysts integrating phosphine ligand and ionic liquid by utilizing the characteristics of designability and easy functionalization of the ionic liquid aiming at the limitations in the prior art, and the integrated catalyst not only has chiral induction capability of the chiral catalyst, but also is ionic liquid and has the functions of ionic liquid dissolution and carrier. Compared with the traditional chiral catalyst used in the prior art, the integrated catalyst has the advantages that: (1) The chiral catalyst has a low melting point (generally 10-60 ℃ or no melting point), belongs to a class of functionalized ionic liquid, and is not an ionic liquid, but a traditional chiral catalyst has a high melting point (generally higher than 100 ℃); (2) The catalyst has a carrier function, can realize separation, recovery and circulation of the catalyst, and the traditional chiral catalyst does not have the capability; (3) The sulfonated phosphine ligand metal chiral catalyst is easy to dissolve in most polar solvents, such as water, methanol, ethanol, isopropanol, acetonitrile, acetone, tetrahydrofuran and dioxane, and also is easy to dissolve in partial weak polar solvents, such as chloroform, dichloromethane, benzene, toluene and the like, so that the application range of the sulfonated phosphine ligand metal chiral catalyst is greatly expanded, and the sulfonated phosphine ligand metal chiral catalyst is generally only soluble in water and is suitable for water/organic two-phase hydrogenation reaction. The sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst has the potential of being applied to asymmetric hydrogenation reactions, such as asymmetric hydrogenation reactions of keto ester.
In order to achieve the purpose of the invention, the chiral catalyst integrating the phosphine ligand and the polyether functionalized ionic liquid has the following structural formula:
chiral catalyst 7 is M (X) 2 (BINAP-(SO 3 A) k ) Which is a mixture of 3 and 4 in any ratio, 3<k<4；
Chiral catalyst 8 is [ M (X) n (Q)(BINAP-(SO 3 A) k )]Y, which is a mixture of 5 and 6 in any ratio, 3<k<4; BINAP- (SO) in 1 or 2 3 A) 2 Represents a chiral phosphine ligand, the structural formula of which is as follows,
3 and 5 BINAP- (SO) 3 A) 4 Represents a chiral phosphine ligand having the formula:
BINAP- (SO) in 4 and 6 3 A) 3 Represents a chiral phosphine ligand having the formula:
wherein the stereo configuration of the chiral phosphine ligand is S type or R type;
a represents an organic onium salt cation having the following structural formula,
wherein m =4-140,R 1 Is C 1 –C 12 Alkyl or phenyl, l =0-140,R 2 Is C 1 –C 12 Alkyl or phenyl; r 3 Is C 1 -C 4 A linear alkyl group; r 4 Is H or C 1 -C 4 A linear alkyl group;
in 1, 3, 4 and 7: m is positive divalent Ru Ⅱ X = Cl, br or I;
in 2, 5, 6 and 8: n =1,M is a positive divalent Ru Ⅱ X = Cl, br or I, Q is benzene (C) 6 H 6 ) Ligand or p-cymene (p-MeC) 6 H 4 CHMe 2 ) Ligand, Y = Cl, br or I.
Detailed Description
Example 1
Catalyst 1a-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and S-BINAP- (SO) were added under argon 3 A) 2 Dissolved in acetone, then 40% hydrobromic acid is added, the molar ratio of hydrobromic acid to ruthenium is 2.
Example 2
Catalysts 1a-2: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 70 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and S-BINAP- (SO) were added under argon 3 A) 2 Dissolved in acetone and then 40% hydrobromic acid is added, the molar ratio of hydrobromic acid to ruthenium being 2Stirring for 30min, removing acetone under reduced pressure to obtain chiral catalyst which is red brown waxy solid at room temperature, and heating to 50-60 deg.C to melt to obtain viscous liquid.
Example 3
Catalysts 1a-3: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) (A = [ n-C) 12 H 25 (OCH 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝n-C 12 H 25 ,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and S-BINAP- (SO) were added under an argon atmosphere 3 A) 2 Dissolved in acetone, then 40% hydrobromic acid is added, the molar ratio of hydrobromic acid to ruthenium is 2.
Example 4
Catalysts 1a-4: ru (Br) 2 (R-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and R-BINAP- (SO) were added under argon 3 A) 2 Dissolved in acetone, then 40% hydrobromic acid was added, the molar ratio of hydrobromic acid to ruthenium was 2.
Example 5
Catalyst 2a-1: [ RuI (p-Cymene) (S-BINAP- (SO) 3 A) 2 )]Synthesis of I (A = [ CH ] 3 (OCH 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝CH 3 ,R 2 ＝CH 3 )
Diiodo (p-cymene) ruthenium (II) dimer ([ RuI) under argon atmosphere 2 (p-Cymene)] 2 ) And S-BINAP- (SO) 3 A) 2 Dissolved in EtOH-CH 2 Cl 2 In (EtOH/CH) 2 Cl 2 = 4/1), molar ratio of the two is 1, stirring at 50 ℃ for 40min, removing the solvent under reduced pressure to obtain chiral catalyst, which is a reddish brown viscous liquid at room temperature.
Example 6
Catalyst 1b-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ (N- (CH)) 2 CH 2 O) 16 Ph)Py] + ,m＝16,R 1 ＝Ph)
Catalyst 1b-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 7
Catalyst 1c-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 NEt 3 ] + ,m＝16,R 1 ＝Ph,R 3 ＝Et)
Catalyst 1c-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 8
Catalyst 1d-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 PEt 3 ] + ,m＝16,R 1 ＝Ph,R 3 ＝Et)
Catalyst 1d-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 9
Catalyst 1e-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 TMG] + ,m＝16,R 1 ＝Ph,R 4 ＝H)
Catalyst 1e-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 10
Catalyst 1f-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Is/are as followsSynthesis (A = [ (N- (CH) = 2 CH 2 O) 16 Ph)(N-CH 3 )Pi] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Catalyst 1f-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 11
Catalyst 1g-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ (N- (CH)) 2 CH 2 O) 16 Ph)(N-CH 3 )Mor] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Catalyst 1g-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 12
Catalyst 1h-1: ru (Br) 2 (S-BINAP-(SO 3 A) 2 ) Synthesis of (A = [ (N- (CH)) 2 CH 2 O) 16 Ph)(N-CH 3 )Pyrr] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Catalyst 1h-1 was prepared according to the synthetic method of example 1, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 13
Catalyst 7a-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (1) (k =3.5, a = [ Ph (OCH) ] 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and S-BINAP- (SO) were added under an argon atmosphere 3 A) 3.5 Dissolved in acetone, then 40% hydrobromic acid is added, the molar ratio of hydrobromic acid to ruthenium is 2.
Example 14
Catalyst 8a-1: [ RuI (p-Cymene) (S-BINAP- (SO) 3 A) 3.5 )]Synthesis of I (k =3.5, a = [ CH ] 3 (OCH 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝CH 3 ,R 2 ＝CH 3 )
Diiodo (p-cymene) ruthenium (II) dimer ([ RuI) under argon atmosphere 2 (p-Cymene)] 2 ) And S-BINAP- (SO) 3 A) 3.5 Dissolved in EtOH-CH 2 Cl 2 In (EtOH/CH) 2 Cl 2 = 4/1), molar ratio of the two is 1, stirring at 50 ℃ for 40min, removing the solvent under reduced pressure to obtain chiral catalyst, which is a reddish brown viscous liquid at room temperature.
Example 15
Catalyst 7b-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (a) = [ (N- (CH) = k =3.5 2 CH 2 O) 16 Ph)Py] + ,m＝16,R 1 ＝Ph)
Catalyst 7b-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 16
Catalyst 7c-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (1) (k =3.5, a = [ Ph (OCH) ] 2 CH 2 ) 16 NEt 3 ] + ,m＝16,R 1 ＝Ph,R 3 ＝Et)
Catalyst 7c-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 17
Catalyst 7d-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (1) (k =3.5, a = [ Ph (OCH) ] 2 CH 2 ) 16 PEt 3 ] + ,m＝16,R 1 ＝Ph,R 3 ＝Et)
Catalyst 7d-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 18
Catalyst 7e-1：Ru(Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (k =3.5, a = [ Ph (OCH) ] 2 CH 2 ) 16 TMG] + ,m＝16,R 1 ＝Ph,R 4 ＝H)
Catalyst 7e-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 19
Catalyst 7f-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (a) = [ (N- (CH) = k =3.5 2 CH 2 O) 16 Ph)(N-CH 3 )Pi] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Catalyst 7f-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 20
Catalyst 7g-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (a) = (k =3.5, a = [ (N- (CH) = 2 CH 2 O) 16 Ph)(N-CH 3 )Mor] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Catalyst 7g-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 21
Catalyst 7h-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3.5 ) Synthesis of (a) = [ (N- (CH) = k =3.5 2 CH 2 O) 16 Ph)(N-CH 3 )Pyrr] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Catalyst 7h-1 was prepared according to the synthetic method of example 13, and the resulting chiral catalyst was a reddish brown viscous liquid at room temperature.
Example 22
Catalyst 3a-1: ru (Br) 2 (S-BINAP-(SO 3 A) 4 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and S-BINAP- (SO) were added under argon 3 A) 4 Dissolved in acetone, then 40% hydrobromic acid was added, the molar ratio of hydrobromic acid to ruthenium was 2.
Example 23
Catalyst 4a-1: ru (Br) 2 (S-BINAP-(SO 3 A) 3 ) Synthesis of (A = [ Ph (OCH) ] 2 CH 2 ) 16 IMCH 3 ] + ,m＝16,l＝0,R 1 ＝Ph,R 2 ＝CH 3 )
Equimolar amounts of bis (2-methylallyl) -1, 5-cyclooctadiene ruthenium and S-BINAP- (SO) were added under an argon atmosphere 3 A) 3 Dissolved in acetone, then 40% hydrobromic acid was added, the molar ratio of hydrobromic acid to ruthenium was 2.
Claims (1)
1. A sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst is characterized in that: the structural formulas of the chiral catalysts 1, 2, 3, 4, 5 and 6 are as follows:
chiral catalyst 7 is M (X) 2 (BINAP-(SO 3 A) k ) Which is a mixture of 3 and 4 in any ratio, 3<k<4；
Chiral catalyst 8 is [ M (X) n (Q)(BINAP-(SO 3 A) k )]Y, which is a mixture of 5 and 6 in any ratio, 3<k<4；
BINAP- (SO) in 1 or 2 3 A) 2 Represents a chiral phosphine ligand having the following structural formula:
3 and 5 BINAP- (SO) 3 A) 4 Represents a chiral phosphine ligand having the formula:
BINAP- (SO) in 4 and 6 3 A) 3 Represents a chiral phosphine ligand having the following structural formula:
wherein the stereo configuration of the chiral phosphine ligand is S type or R type;
a represents an organic onium salt cation having the following structural formula:
wherein m =4-140,R 1 Is C 1 –C 12 Alkyl or phenyl, l =0-140,R 2 Is C 1 –C 12 Alkyl or phenyl; r 3 Is C 1 -C 4 A linear alkyl group; r 4 Is H or C 1 -C 4 A linear alkyl group;
in 1, 3, 4 and 7: m is positive divalent Ru Ⅱ X = Cl, br or I;
in 2, 5, 6 and 8: n =1,M is a positive divalent Ru Ⅱ X = Cl, br or I, Q is benzene (C) 6 H 6 ) Ligands or p-cymene (p-MeC) 6 H 4 CHMe 2 ) Ligand, Y = Cl, br or I.
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