Preparation method of supported ferrocene ligand

Abstract

The invention relates to a preparation method of a supported ferrocene ligand, and the preparation method of the supported ferrocene ligand comprises the following steps: loading a ferrocene ligand or a complex of the ferrocene ligand and metal on a carrier through Friedel-Crafts alkylation reaction under the condition of Lewis acid and a solvent, on the basis of Friedel-Crafts alkylation reaction, a commercially available carrier is selected, an expensive ferrocene ligand is loaded on the carrier with a controllable structure and stable mechanical property through a one-step method, and the ferrocene ligand with different structures has better tolerance. The loaded ferrocene catalyst is easy to regulate and control in physical property and stable in chemical property, and has great industrial application potential.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, in particular to a method for preparing a supported ferrocene ligand. Background Art

[0002] Ferrocene ligands are widely used as catalysts in the synthesis reactions of various chiral ligands and porous materials, as well as in the construction reactions of chiral carbon-nitrogen, carbon-oxygen, carbon-hydrogen, carbon-sulfur, and carbon-phosphorus bonds, due to their special planar chiral structure and stable physical and chemical properties. Therefore, ferrocene ligands play a very important role in the synthesis of chiral compounds.

[0003] However, due to the relatively complex structure of ferrocene ligands, synthesis and purification may be difficult, resulting in the high price of such ligands. At the same time, because ferrocene ligands are usually used as homogeneous catalysts, that is, ferrocene ligands and reactants are dissolved in the same solvent to form a uniform solution system, this means that ferrocene ligands are difficult to recycle during the catalytic reaction, which greatly increases the cost of such catalytic reactions. Therefore, it is still very challenging to apply such ligands with wide catalytic activity and wide application to industrial production.

[0004] Ferrocene ligands can usually be loaded on solid carriers. The loaded ferrocene ligand catalyst is usually solid particles, which are easy to separate and recover from the reaction mixture. This can greatly reduce the cost of the catalyst and enable it to be reused in multiple reaction cycles, thereby increasing the economy of the catalyst.

[0005] At present, there are many problems in the loading of ferrocene ligands: the loading process is mostly complicated, and the structure of ferrocene ligands can include various functional groups, such as carboxylic acid, aldehyde, amine, phosphine, alkyl, etc. The chemical properties of these functional groups vary greatly, and different reaction conditions (such as temperature, pH value, catalyst, solvent, etc.) are required for modification, which further increases the production cost of the ligand. Summary of the invention

[0006] Based on this, it is necessary to provide a method for preparing a supported ferrocene ligand which is simple, low-cost and has a universal loading method.

[0007] To achieve the above object, the present invention provides a technical solution:

[0008] A method for preparing a supported ferrocene ligand comprises the following steps: loading the ferrocene ligand or a complex of the ferrocene ligand and a metal on a carrier by Friedel-Crafts alkylation reaction under the conditions of Lewis acid and solvent;

[0009] Wherein, the structural formula of the carrier is

[0010] The structural formula of the ferrocene ligand is

[0011] R1 is methyl or hydrogen;

[0012] R2 is hydrogen, 3,5-dimethyl or 4-methyl;

[0013] X is oxygen or sulfur;

[0014] The range of a is 1 to 99;

[0015] The range of b is 1 to 99.

[0016] In some embodiments, the reaction formula of Friedel-Crafts alkylation reaction is as follows:

[0017]

[0018] Wherein, the ferrocene ligand includes at least one of L1, L2, L3, L4, L5 and L6, and its structural formula is as follows:

[0019]

[0020] In some embodiments, the reaction formula of Friedel-Crafts alkylation reaction is as follows:

[0021]

[0022] Wherein, the ferrocene ligand includes at least one of L7, L8, L9, L10, L11 and L12, and its structural formula is as follows:

[0023]

[0024] In some embodiments, the crosslinking agent includes at least one of dimethoxymethane, 1,4-dichloromethylbenzene, 1,4-dibenzylmethoxybenzene, dichloromethane, chloroform, (4,4')-chloromethylbiphenyl, and (4,4')-benzylmethoxybiphenyl.

[0025] In some embodiments, the metal includes [Rh(cod)Cl]2, [Ir(cod)Cl]2, [Rh(cod)2]BF4, [Rh(cod)2]SbF 6、 At least one of [Rh(nbd)]2BF4 and [Rh(cod)2]BARF.

[0026] In some embodiments, R includes at least one of divinylphenyl, 1,3-butadienyl, isoprenyl, ethylene-trans-butenyl, acryl, and styryl, and derivatives thereof.

[0027] In some embodiments, the reaction temperature of the Friedel-Crafts alkylation reaction is -50°C to 80°C.

[0028] In some embodiments, the reaction time of the Friedel-Crafts alkylation reaction is 0.5-12 hours.

[0029] In some embodiments, the solvent includes at least one of dichloromethane, tetrahydrofuran, N,N-dimethylformamide, ethyl acetate, petroleum ether, diethyl ether, chloroform, 1,2-dichloroethane, nitromethane, nitrobenzene and carbon tetrachloride.

[0030] In some embodiments, the Lewis acid includes at least one of aluminum trichloride, hydrochloric acid, phosphoric acid, boron trifluoride, ferric chloride, tin tetrachloride, concentrated sulfuric acid, and trifluoromethanesulfonic acid.

[0031] Beneficial effects of the present invention:

[0032] The present invention is based on Friedel-Crafts alkylation reaction, selects commercially available carriers, and loads expensive ferrocene ligands onto carriers with controllable structures and stable mechanical properties through a one-step method, and has good tolerance for ferrocene ligands with different structures.

[0033] The physical properties of supported ferrocene ligand catalysts are easy to control and their chemical properties are stable. They have great potential for industrial application and can be used in the synthesis reactions of various chiral ligands and porous materials, as well as in the construction reactions of chiral carbon-nitrogen, carbon-oxygen, carbon-hydrogen, carbon-sulfur, and carbon-phosphorus bonds. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is the reaction equation in some embodiments;

[0035] Figure 2 is a reaction equation in another embodiment. DETAILED DESCRIPTION

[0036] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0037] In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0038] A method for preparing a supported ferrocene ligand comprises the following steps: loading the ferrocene ligand or a complex of the ferrocene ligand and a metal on a carrier by Friedel-Crafts alkylation reaction under the conditions of Lewis acid and solvent;

[0039] Wherein, the structural formula of the carrier is

[0040] The structural formula of the ferrocene ligand is

[0041] R1 is methyl or hydrogen;

[0042] R2 is hydrogen, 3,5-dimethyl or 4-methyl;

[0043] X is oxygen or sulfur;

[0044] The range of a is 1 to 99;

[0045] The range of b is 1 to 99.

[0046] Friedel-Crafts alkylation reaction can connect different aromatic rings together through covalent bonds in a one-step method. Compared with other coupling reactions that require directing groups, Friedel-Crafts alkylation reaction does not require directing groups and has a wide range of substrate functional groups.

[0047] Most of the chiral ligands reported so far are constructed with aromatic rings as the basic skeleton. Therefore, combining the Friedel-Crafts alkylation reaction with the loading of chiral ligands to develop a simple ligand loading method has broad application value and potential industrial application prospects.

[0048] The present invention is based on Friedel-Crafts alkylation reaction, selects commercially available cheap styrene polymer as a carrier, and loads expensive chiral ligands onto the carrier with controllable structure and stable mechanical properties through a one-step method, and has good tolerance for chiral ligands with different structures.

[0049] The physical properties of supported ferrocene ligand catalysts are easy to control and their chemical properties are stable, which shows great potential for industrial application.

[0050] In some embodiments, the reaction equation of Friedel-Crafts alkylation reaction is as follows (eg Figure 1 shown):

[0051]

[0052] Wherein, the ferrocene ligand (L-CF3) includes at least one of L1, L2, L3, L4, L5 and L6, and its structural formula is as follows:

[0053]

[0054] In some embodiments, the reaction equation of Friedel-Crafts alkylation is as follows (eg Figure 2 shown):

[0055]

[0056] Specifically, since there is no trifluoromethyl group on the ferrocene ligand (L-Ar), a cross-linking agent needs to be added for Friedel-Crafts alkylation to occur, otherwise the ligand will not be immobilized.

[0057] Wherein, the ferrocene ligand (L-Ar) includes at least one of L7, L8, L9, L10, L11 and L12, and its structural formula is as follows:

[0058]

[0059] In the present invention, Me: represents a methyl group, and the chemical formula is CH3;

[0060] Ph: stands for phenyl group, and its chemical formula is C6H5.

[0061] In some embodiments, the crosslinking agent includes at least one of dimethoxymethane, 1,4-dichloromethylbenzene, 1,4-dibenzylmethoxybenzene, dichloromethane, chloroform, (4,4')-chloromethylbiphenyl, and (4,4')-benzylmethoxybiphenyl.

[0062] More specifically, the synthesis of SL-CF3:

[0063] Weigh the ligand L-CF3 in a reaction tube at room temperature, replace it with inert gas three times, then add the solvent to dissolve it, add the styrene polymer carrier S after the catalyst is completely dissolved, adjust the reaction solution to an appropriate temperature, add Lewis acid, react at a corresponding temperature (-50-80°C) for a period of time, then add a quencher to quench (quenchers include: anhydrous ethanol, anhydrous methanol, hydrochloric acid aqueous solution or ammonium chloride aqueous solution) to react. Centrifuge or filter the reaction solution, wash the solid with a detergent (detergents include: anhydrous ethanol, dichloromethane, ethyl acetate, anhydrous methanol, petroleum ether, hydrochloric acid aqueous solution, etc.), and then extract with anhydrous ethanol or dichloromethane for 48 hours to obtain the supported catalyst SL-CF3.

[0064] Synthesis of SL-Ar:

[0065] Weigh the ligand L-Ar in a reaction tube at room temperature, replace it with inert gas three times, then add a solvent to dissolve it. After the ligand L-Ar is completely dissolved, add the styrene polymer carrier S and the crosslinking agent. Adjust the reaction solution to an appropriate temperature and add Lewis acid. After reacting for a period of time at the corresponding temperature (-50-80°C), add a quencher to quench the reaction (quenchers include: anhydrous ethanol, anhydrous methanol, hydrochloric acid aqueous solution, ammonium chloride aqueous solution, etc.). Centrifuge or filter the reaction solution, wash the solid with a detergent (detergents include: anhydrous ethanol, dichloromethane, ethyl acetate, anhydrous methanol, petroleum ether, hydrochloric acid aqueous solution, etc.), and then extract with anhydrous ethanol or dichloromethane for 48 hours to obtain the supported catalyst SL-Ar.

[0066] In some embodiments, the metal includes [Rh(cod)Cl]2, [Ir(cod)Cl]2, [Rh(cod)2]BF4, [Rh(cod)2]SbF 6、 At least one of [Rh(nbd)]2BF4 and [Rh(cod)2]BARF.

[0067] [Rh(cod)Cl]2 is a dinuclear rhodium(I) complex consisting of two rhodium atoms (Rh) linked together by a chlorine bridge (Cl), each rhodium atom coordinated by two cyclooctadiene (cod) ligands;

[0068] Similar to [Rh(cod)Cl]2, [Ir(cod)Cl]2 is an iridium(I) complex, also composed of two iridium atoms bridged by chlorine, each coordinated with two cyclooctadiene ligands;

[0069] [Rh(cod)2]BF4 is a mononuclear rhodium(I) complex with two cyclooctadiene ligands coordinated to the rhodium center and a tetrafluoroborate (BF4 - ) as anion.

[0070] [Rh(cod)2]SbF6 is similar to [Rh(cod)2]BF4, except that its anion is hexafluoroantimonate (SbF6 - )

[0071] [Rh(nbd)]2BF4 is similar to [Rh(cod)2]BF4, except that its coordination compound is dicyclopentadiene. The ion of [Rh(cod)2]BARF is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, abbreviated as BARF.

[0072] In some embodiments, R includes at least one of divinylphenyl, 1,3-butadienyl, isoprenyl, ethylene-trans-butenyl, acryl, and styryl, and derivatives thereof.

[0073] In some embodiments, the reaction temperature of the Friedel-Crafts alkylation reaction is -50°C to 80°C.

[0074] In some embodiments, the reaction time of the Friedel-Crafts alkylation reaction is 0.5 h to 12 h.

[0075] In some embodiments, the solvent includes at least one of dichloromethane (DCM), chloroform (CF), tetrahydrofuran (THF), N,N-dimethylformamide, ethyl acetate, petroleum ether, diethyl ether, 1,2-dichloroethane (DCE), nitromethane (NM), nitrobenzene (NB) and carbon tetrachloride (CCl4).

[0076] In some embodiments, the Lewis acid includes at least one of aluminum trichloride, hydrochloric acid, phosphoric acid, boron trifluoride, ferric chloride, tin tetrachloride, concentrated sulfuric acid, and trifluoromethanesulfonic acid.

[0077] Example 1

[0078] At room temperature, 30 mg of ferrocene ligand (L1) and 17 mg of metal ([Rh(cod)2]BF4) were weighed into a reaction tube. After the inert gas was replaced three times, 1,2-dichloroethane (2 ml) was added to dissolve. After L1 and [Rh(COD)2]BF4 were completely dissolved, stirring was continued for 60 min. The carrier (the carrier structure formula is wherein a=100, b=1, R is divinylphenyl) 140mg, the reaction solution was cooled to -30℃ and then anhydrous aluminum chloride (50mg) was added, the reaction was continued at -30℃ for 18h and then anhydrous ethanol was added to quench, the reaction solution was slowly heated to room temperature and then filtered, the filter cake was washed alternately with anhydrous ethanol and dichloromethane and then extracted with anhydrous ethanol for 48h to obtain 178mg of supported ferrocene ligand catalyst S-L1 / M-CF3 (M=[Rh(cod)2]BF4). Inductively Coupled Plasma Optical Emission Spectro (ICP-OES) test showed that the Rh loading in the catalyst was 0.041mmol / g and the P loading was 0.098mmol / g.

[0079] Example 2

[0080] At room temperature, 30 mg of ferrocene ligand (L1) was weighed into a reaction tube, and the tube was filled with inert gas for three times, and then dichloromethane (2 ml) was added to dissolve. After L1 was completely dissolved, the carrier (the carrier structure is Where a=100, b=2, R is divinylphenyl 140mg, after cooling the reaction solution to -30℃, add anhydrous aluminum chloride (50mg), react at -30℃ for 18h, add anhydrous ethanol to quench, slowly warm to room temperature and filter, wash the filter cake alternately with anhydrous ethanol and dichloromethane, and extract with anhydrous ethanol for 48h to obtain supported catalyst S-L1-CF3165mg. Then disperse the supported catalyst into 5ml anhydrous DCM, add metal ([Ir(cod)Cl]2) 15mg, stir at room temperature for 1h to obtain supported ferrocene ligand catalyst S-L1 / M-CF3 (M=Ir(cod)Cl]2) 180mg. ICP-OES test shows that the Ir loading in the catalyst is 0.054mmol / g, and the P loading is 0.101mmol / g.

[0081] Example 3

[0082] At room temperature, 30 mg of ferrocene ligand (L5) and 17 mg of metal ([Rh(cod)Cl]2) were weighed into a reaction tube. After the inert gas was replaced three times, chloroform (2 ml) was added. After L5 (30 mg) and [Rh(cod)Cl]2 were completely dissolved, the mixture was stirred at room temperature for 1 hour. The carrier (the carrier structure is wherein a=100, b=1, R is divinylphenyl) 140mg, after cooling the reaction solution to 0℃, add anhydrous aluminum chloride (100mg), react at 0℃ for 4h, add anhydrous ethanol to quench, slowly warm to room temperature and filter, wash the filter cake alternately with anhydrous ethanol and dichloromethane, and then extract with anhydrous ethanol for 48h to obtain 178mg of supported ferrocene ligand catalyst S-L1 / M-CF3 (M=[Rh(cod)Cl]2). ICP-OES test shows that the Rh loading in the catalyst is 0.038mmol / g, and the P loading is 0.112mmol / g.

[0083] Example 4

[0084] At room temperature, ligand L9 (30 mg) was weighed into a reaction tube, and the tube was filled with inert gas for three times, and then chloroform (2 mL) was added. After the catalyst was completely dissolved, the carrier (the carrier structure is Wherein a=100, b=0, R is styryl) 70mg and 20uL dimethoxymethane. Add tin tetrachloride (100mg) to the reaction solution at room temperature, react at room temperature for 8h, add hydrochloric acid aqueous solution to quench, filter, wash the filter cake alternately with anhydrous ethanol and dichloromethane, and extract the solid with dichloromethane Soxhlet for 48h to obtain 92mg of supported catalyst S-L9-Ar. Disperse the obtained supported catalyst into 5mL of anhydrous DCM, add [Rh(cod)2]BARF (15mg), stir at room temperature for 1h to obtain supported ferrocene ligand catalyst S-L1 / M-CF3 (M=[Rh(cod)2]BARF), 105mg. ICP-OES test shows that the Rh loading in the catalyst is 0.011mmol / g, and the P loading is 0.032mmol / g.

[0085] Example 5

[0086] At room temperature, 30 mg of ferrocene ligand (L11) was weighed into a reaction tube, and the tube was filled with inert gas for three times, and then nitrobenzene (2 mL) was added. After the ferrocene ligand was completely dissolved, the carrier (the carrier structure is Wherein a=22, b=78, R is isoprene) 80mg and 4,4'-dichloromethylbiphenyl 50mg. Trifluoromethanesulfonic acid (100uL) was added to the reaction solution at room temperature, stirred and heated to 80℃ for 24h, then methanol was added to quench, filtered, the filter cake was washed alternately with anhydrous ethanol and dichloromethane, and the solid was extracted with anhydrous ethanol Soxhlet for 48h to obtain 100mg of supported catalyst S-L11-Ar. The obtained supported catalyst was dispersed in 5ml of anhydrous DCM, [Ir(cod)Cl]2 (18mg) was added, and 115mg of supported ferrocene ligand catalyst S-L11 / M-Ar (M=[Ir(cod)Cl]2) was obtained after stirring at room temperature for 1h. ICP-OES test showed that the Ir loading in the catalyst was 0.061mmol / g and the P loading was 0.128mmol / g.

[0087] The success of the Friedel-Crafts alkylation reaction depends on the rational selection and optimization of the carrier, solvent, reaction temperature and Lewis acid. A carrier with good aromaticity, stability and pore structure, as well as a non-polar or weakly polar solvent, helps to improve the reaction efficiency and selectivity. A moderate reaction temperature helps to avoid side reactions, while a strong Lewis acid catalyst promotes the alkylation reaction by activating an electrophilic reagent. The combined effect of these factors determines the efficiency, selectivity and purity of the product of the reaction. Therefore, the present invention is as follows for the rational selection and optimization of solvents, reaction temperatures and Lewis acids:

[0088] Comparative Example 1

[0089] At room temperature, 30 mg of ferrocene ligand (L1) was weighed into a reaction tube, and the tube was filled with inert gas for three times, and then dichloromethane (2 ml) was added to dissolve. After L1 was completely dissolved, the carrier (the carrier structure is Where a=100, b=1, R is 140mg of divinylphenyl, after cooling the reaction solution to -30℃, add anhydrous aluminum chloride (50mg), react at -70℃ for 18h, add anhydrous ethanol to quench, slowly warm to room temperature and filter, wash the filter cake alternately with anhydrous ethanol and dichloromethane, and then extract with anhydrous ethanol Soxhlet for 48h to obtain a white powdery solid. ICP-OES test shows that the P loading in the catalyst is 0.005mmol / g. Because the catalyst itself is yellow, the loaded catalyst obtained after combining with the carrier should be yellow. This time, a white solid was obtained, which means that the reaction temperature is too low, the catalyst cannot react with the carrier, and the reaction conditions are not suitable.

[0090] Comparative Example 2

[0091] At room temperature, 30 mg of ferrocene ligand (L1) was weighed into a reaction tube, and the tube was filled with inert gas for three times, and then anhydrous ethanol (2 ml) was added. After L1 was completely dissolved, the carrier (the carrier structure is 140 mg of a (wherein a=90, b=10, R is divinylphenyl) was added to anhydrous aluminum chloride (50 mg) at room temperature. After the addition of aluminum chloride, a large amount of white smoke emerged from the reaction solution, and heat was released seriously. ICP-OES test showed that the P loading in the catalyst was 0.006 mmol / g.

[0092] This is because aluminum chloride is a protic solvent and reacts with anhydrous ethanol. Therefore, this reaction is not suitable for using protic solvents such as anhydrous ethanol.

[0093] Comparative Example 3

[0094] At room temperature, 30 mg of ferrocene ligand (L5) and 17 mg of metal ([Rh(cod)Cl]2) were weighed into a reaction tube. After the inert gas was replaced three times, chloroform (2 ml) was added. After L5 (30 mg) and [Rh(cod)Cl]2 were completely dissolved, the mixture was stirred at room temperature for 1 hour. The carrier (the carrier structure is The reaction solution was cooled to 0°C and then 0.5 ml of 4M tetrahydrofuran hydrochloride was added. After reacting at 0°C for 4 hours, the mixture was slowly heated to room temperature and filtered to obtain a white powdery solid. ICP-OES test showed that the Rh loading in the catalyst was 0.002 mmol / g and the P loading was 0.010 mmol / g.

[0095] The 4M tetrahydrofuran hydrochloride refers to a solution of hydrochloric acid (HCl) having a concentration of 4 moles per liter (4 M) dissolved in tetrahydrofuran (THF).

[0096] This is because hydrochloric acid is not suitable for catalyzing the reaction, resulting in poor reaction between the ligand and the carrier.

[0097] Application of supported ferrocene ligand catalysts

[0098] The prepared supported ferrocene ligand catalyst is used in the heterogeneous asymmetric synthesis reaction of chiral benzoxazinone and its derivatives, wherein the supported ferrocene ligand catalyst (SL-CF3) has the following structural formula:

[0099] Wherein, a=100, b=1, R=divinylbenzene;

[0100] The heterogeneous asymmetric synthesis reaction equation of chiral benzoxazinone and its derivatives is as follows:

[0101]

[0102] The specific reaction steps are as follows:

[0103] Weigh SL-CF3 (20 mg, 1 mmol%) and quinoxaline derivative (27 mg, 0.5 mmol) in a reaction tube, move to a glove box, add 2 ml of anhydrous ethanol and a dioxane solution of hydrochloric acid (2 M), stir at room temperature for 10 min, then move out of the glove box, fill with hydrogen to 5 MPa, react at room temperature for 16 h, then release the pressure, filter, wash the filter cake with ethyl acetate, and evaporate the filtrate to dryness under reduced pressure to obtain the target product. No further purification is required and it is directly detected. The nuclear magnetic conversion rate is greater than 99%.

[0104] HPLC: ee=98%, AD H-15-85-1-30, RT 11.56 / 17.82min.

[0105] 1H NMR(400MHz,Chloroform-d)δ7.44–7.34(m,5H),7.08–7.00(m,2H),6.87(td,J=7.8,1.4Hz,1H),6.82(dd,J=7.8,1.3Hz,1H),5.07(s,1H),4.27(s,1H).13C NMR (101MHz, CDCl3) δ165.35,141.02,136.46,132.49,129.13,127.62,125.32,120.53,117.12,114.99,59.41,29.83.

[0106] To verify that the supported ferrocene ligand catalyst can be recycled, the filter cake was vacuum dried at 40°C for 24 hours and used for the next cycle (the steps are the same as the above steps). The cycle was repeated 5 times, and the results are shown in Table 1.

[0107] Table 1 Cycle results

[0108] Cycle times Yield ee 1 99 98 2 99 97 3 99 98 4 95 84 5 88 86

[0109] It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments of the present invention, rather than limiting the present invention; those skilled in the art can make adaptive adjustments within the scope of the present invention.

Claims

1. A method for preparing a supported ferrocene ligand, characterized in that: The preparation method of the supported ferrocene ligand comprises the following steps: under the conditions of Lewis acid and solvent, a ferrocene ligand or a complex of a ferrocene ligand and a metal is loaded on a carrier by Friedel-Crafts alkylation reaction to obtain a supported ferrocene ligand; Wherein, the structural formula of the carrier is The structural formula of the ferrocene ligand is R is a conjugated olefin group; R1 is methyl or hydrogen; R2 is hydrogen, 3,5-dimethyl or 4-methyl; X is oxygen or sulfur; The range of a is 1 to 99; The range of b is 1 to 99.

2. The method for preparing a supported ferrocene ligand according to claim 1, wherein The reaction equation of Friedel-Crafts alkylation is as follows: Wherein, the ferrocene ligand includes at least one of L1, L2, L3, L4, L5 and L6, and its structural formula is as follows:

3. The method for preparing a supported ferrocene ligand according to claim 1, wherein The reaction equation of Friedel-Crafts alkylation is as follows: Wherein, the ferrocene ligand includes at least one of L7, L8, L9, L10, L11 and L12, and its structural formula is as follows:

4. The method for preparing a supported ferrocene ligand according to claim 3, wherein: The crosslinking agent includes at least one of dimethoxymethane, 1,4-dichloromethylbenzene, 1,4-dibenzylmethoxybenzene, dichloromethane, chloroform, (4,4')-chloromethylbiphenyl and (4,4')-benzylmethoxybiphenyl.

5. The method for preparing a supported ferrocene ligand according to claim 1, wherein Metals include [Rh(cod)Cl]2, [Ir(cod)Cl]2, [Rh(cod)2]BF4, [Rh(cod)2]SbF 6、 At least one of [Rh(nbd)]2BF4 and [Rh(cod)2]BARF.

6. The method for preparing a supported ferrocene ligand according to claim 1, wherein R includes at least one of divinylphenyl, 1,3-butadienyl, isoprenyl, ethylene-trans-butenyl, acryl, styryl and derivatives thereof.

7. The method for preparing a supported ferrocene ligand according to claim 1, characterized in that: The reaction temperature of the Friedel-Crafts alkylation reaction is -50°C to 80°C.

8. The method for preparing a supported ferrocene ligand according to claim 1, wherein The reaction time of the Friedel-Crafts alkylation reaction is 0.5h to 12h.

9. The method for preparing a supported ferrocene ligand according to claim 1, characterized in that: The solvent includes at least one of dichloromethane, tetrahydrofuran, N,N-dimethylformamide, ethyl acetate, petroleum ether, ethyl ether, chloroform, 1,2-dichloroethane, nitromethane, nitrobenzene and carbon tetrachloride.

10. The method for preparing a supported ferrocene ligand according to claim 1, characterized in that: The Lewis acid includes at least one of aluminum trichloride, hydrochloric acid, phosphoric acid, boron trifluoride, ferric chloride, tin tetrachloride, concentrated sulfuric acid and trifluoromethanesulfonic acid.

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