CN113354552B - Synthetic method of V-type organic ligand, synthetic V-type organic ligand and application thereof - Google Patents
Synthetic method of V-type organic ligand, synthetic V-type organic ligand and application thereof Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a V-shaped organic ligand, which relates to the technical field of organic ligands and comprises the following steps: the method comprises the following steps of taking a raw material A and a raw material B as raw materials, taking 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole and N, N-diisopropylethylamine as catalysts, taking N, N-dimethylformamide as a solvent, reacting for 48 hours at room temperature, and purifying a reaction mixture to obtain a product. The invention also provides a V-type organic ligand synthesized by the method and application thereof. The invention has the advantages that: the organic ligand can be applied to asymmetric addition catalysis or a synthetic substrate of a novel MOFs catalyst, can also be used as a medical intermediate product, and provides a new idea for the synthesis of the same type of V-type ligand.
Description
Technical Field
The invention relates to the technical field of organic ligands, in particular to a synthetic method of a V-shaped organic ligand, the synthetic V-shaped organic ligand and application thereof.
Background
The Metal Organic Framework, abbreviated as MOFs (Metal Organic Framework), is a zeolite material with a spatial porous structure composed of Organic ligands (linkers) and Metal ions or clusters (nodes), which has the characteristics of an Organic-inorganic hybrid material and is also a coordination polymer. Because of the advantages of both organic and inorganic materials, it is a promising material in heterogeneous catalysis, and has important applications in the fields of photocatalysis, biomedicine, gas adsorption and separation, etc. Since the synthesis of the first class of MOF compounds in 1995 to date, over eight thousand metal-organic framework materials have been synthesized. By designing the organic ligand (connector), proper metal ions can be selected for combination, so that the coordination polymer with special topological structure and performance can be constructed.
The currently known coordination polymers are mainly classified into three types according to organic ligands, namely coordination polymers containing carboxylic acid ligands, coordination polymers containing nitrogen ligands and coordination polymers containing sulfur and phosphorus ligands, and the coordination compounds of carboxylic acid systems are the coordination compounds with large specific gravity which are currently put into research. Most of the carboxylic acid ligands are simple compounds which are easy to prepare or natural compounds which are easy to obtain, but the synthesis of the complex organic ligands still has many problems, such as harsh reaction conditions, unclear synthetic route, difficult post-treatment and the like, and the V-type organic ligands with complex structures are difficult to synthesize.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing a novel V-shaped organic ligand in the prior art, the prepared V-shaped organic ligand can be used as a catalyst for the asymmetric addition reaction of aryl boric acid to olefin, and the synthesized product has high chemical selectivity and chiral selectivity.
The invention solves the technical problems through the following technical means:
a method for synthesizing a V-type organic ligand comprises the following steps: taking raw material A (1R, 4R, 7R) -7-isopropyl-5-methyl bicyclo [2.2.2] octa-2, 5-diene-2-carboxylic acid and raw material B3, 5-di (4-methoxy carbonyl phenyl) aniline as raw materials, 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride (EDCI), 1-hydroxybenzotriazole (HOBt) and N, N-diisopropyl ethylamine (DIEA) as catalysts, reacting at room temperature by taking N, N-dimethyl formamide (DMF) as a solvent, and purifying a reaction mixture to obtain a V-type organic ligand;
has the advantages that: the synthesis method is simple, and the V-type organic ligand is obtained by amidating the two raw materials. The reaction can be carried out at room temperature, the reaction operation is simple and convenient, and the reaction process is green and safe.
The V-type ligand designed and synthesized by the invention can be used as a catalyst for asymmetric addition of aryl boric acid to olefin at present, and the synthesized product has high chemical selectivity and chiral selectivity. Meanwhile, the catalyst is hopeful to be combined with proper metal ions (such as rhodium) to synthesize a special MOFs catalyst, and can be applied to homogeneous and heterogeneous catalysis. Can also be used as a medical intermediate product. The synthesis of the V-type ligand also provides a new idea for the synthesis of the compounds of the same type.
Preferably, the catalyst content required for the reaction is: the adding molar weight of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the 1-hydroxybenzotriazole is 1.2 times of that of the raw material A; the molar weight of the N, N-diisopropylethylamine is 2.5 times that of the raw material A.
Preferably, the purification of the reaction mixture comprises the steps of: acidifying the reaction mixture by dilute hydrochloric acid, extracting by ethyl acetate, detecting by thin-layer chromatography, and purifying and separating by column chromatography to obtain the V-type organic ligand.
Preferably, the synthesis method of the raw material A comprises the following steps:
(1) Taking propiolic acid and 2-naphthol as raw materials, 4-Dimethylaminopyridine (DMAP) and Dicyclohexylcarbodiimide (DCC) as catalysts, and dichloromethane as a solvent, adding in ice bath, and reacting at room temperature for 5 hours to obtain 2-naphthyl propiolate shown in a formula IV;
(2) Then taking a product shown in a formula IV and (R) -alpha-phellandrene as raw materials, and taking dimethyl aluminum chloride (Me) 2 AlCl) is used as a catalyst, dichloromethane is used as a solvent, and after the materials are added at-78 ℃, the materials react for 18 hours at room temperature to obtain a product shown in a formula III;
(3) Performing ester exchange on the product shown in the formula III, and reacting in a methanol solvent for 24 hours at room temperature under the catalysis of potassium carbonate to obtain a product shown in a formula II, wherein the product shown in the formula II is hydrolyzed to obtain a product shown in a formula I, namely a raw material A;
preferably, the amount of catalyst required during the synthesis of the product of formula IV is: adding 4-dimethylamino pyridine with the molar weight of 1% of that of 2-naphthol; the molar amount of dicyclohexylcarbodiimide was 1.1 times that of 2-naphthol.
Preferably, the amount of catalyst required during the synthesis of the product of formula iii is: dimethyl aluminum chloride was added in a molar amount of 1.1 times that of the product represented by formula IV.
Preferably, the synthesis method of the raw material B comprises the following steps: 3, 5-dichloroaniline and 4-methoxycarbonylphenylboronic acid are taken as raw materials, palladium acetate, potassium phosphate and Ruphos are taken as catalysts, anhydrous THF is taken as a solvent, and the raw materials are refluxed for 5 hours at 75 ℃ under the anhydrous and oxygen-free conditions to obtain a raw material B;
has the advantages that: the invention shortens the two-step reaction into one-step reaction and optimizes the reaction conditions.
Preferably, the Ruphos is 2-dicyclohexyl-2 ',6' -diisopropoxy-1, 1' -biphenyl, which has the following structural formula:
preferably, the catalyst content required for the reaction is: the adding molar weight of the palladium acetate is 2 percent of that of the 3, 5-dichloroaniline; ruphos molar amount is 5% of 3, 5-dichloroaniline; the molar weight of potassium phosphate is 3-5 times of that of 3, 5-dichloroaniline.
The invention also provides a V-type organic ligand synthesized by the method.
Has the advantages that: the V-type ligand can be used as a catalyst to be applied to asymmetric addition of aryl boric acid to olefin, and the synthesized product has high chemical selectivity and chiral selectivity. Meanwhile, the catalyst is hopeful to be combined with proper metal ions (such as rhodium) to synthesize a special MOFs catalyst, and can be applied to homogeneous and heterogeneous catalysis. Can also be used as a medical intermediate product. The synthesis of the V-type ligand also provides a new idea for the synthesis of the compounds of the same type.
The invention also provides application of the V-shaped organic ligand synthesized by the method as a catalyst in catalyzing asymmetric addition reaction.
Has the advantages that: the product of catalytic synthesis has high chemical selectivity and chiral selectivity.
Preferably, the V-type organic ligand is used as a catalyst to catalyze the asymmetric addition reaction of aryl boric acid to olefin.
Preferably, the asymmetric addition reaction comprises the steps of: mixing olefin and arylboronic acid, adding a V-type organic ligand, adding a potassium hydroxide methanol solution, carrying out sealing reaction at 80 ℃, and purifying to obtain a product.
Preferably, the olefin comprises 5-methyl-3-ethen-2-one, 2-cyclohexenone or 2-cyclopentenone.
The invention has the advantages that: the synthesis method is simple, and the V-type organic ligand is obtained by amidating the two raw materials. The reaction can be carried out at room temperature, the reaction operation is simple and convenient, and the reaction process is green and safe.
The processes (such as Diels-Alde cycloaddition, suzuki coupling and the like) of the reaction of the invention are mature reactions, and do not involve complex reactions.
The V-type ligand designed and synthesized by the invention can be used as a catalyst for asymmetric addition of aryl boric acid to olefin at present, and the synthesized product has high chemical selectivity and chiral selectivity. Meanwhile, the catalyst is hopeful to be combined with proper metal ions (such as rhodium) to synthesize a special MOFs catalyst, and can be applied to homogeneous and heterogeneous catalysis. Can also be used as a medical intermediate product. The synthesis of the V-type ligand also provides a new idea for the synthesis of the compounds of the same type.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
Synthesis of starting Material A
The synthesis scheme and the specific steps of the product (IV) are as follows:
a clean 150ml round bottom flask was taken, placed under a magnetic stir bar of appropriate size, 2-naphthol (2g, 13.87mmol), 4-dimethylaminopyridine (DMAP, 16.9mg, 0.139mmol) and dichloromethane (20 ml) were added, propiolic acid (1.07g, 15.26mmol) was added to the solution and the round bottom flask was placed in an ice-water bath, dicyclohexylcarbodiimide (DCC, 3.15g, 15.26mmol) was added dropwise to the solution at 0 deg.C, and after the solution had returned to room temperature, stirring was continued for 5h. The reaction mixture was filtered, the filtrate collected, concentrated in vacuo, and chromatographed (petroleum ether: ethyl acetate =200: 1) to give product (IV) as a white solid (1.3 g, 47.8%).
1 H NMR(600MHz,Chloroform-d)δ7.89–7.80(m,3H),7.63(d,J＝2.3Hz,1H),7.50(pd,J＝6.9,1.5Hz,2H),7.28(d,J＝2.4Hz,1H),3.10(s,1H).
The synthesis process and specific steps of the product (III) are as follows:
a round-bottomed flask was charged with a stirrer, and then 2-naphthylpropiolate (1.96g, 10mmol) and (R) - α -phellandrene (1.53g, 11mmol) were added to CH at-78 deg.C 2 Cl 2 Slow addition of Me to the solution 2 AlCl (10.17g, 11mmol, 1M), warmed to room temperature and stirred for 18h. Pouring the solution into ice-cooled and vigorously stirred dilute HCl solution, standing and filtering, and then using CH 2 Cl 2 (3X 10 ml) washing, CH 2 Cl 2 The extract was washed with saturated brine, dried, filtered and concentrated in vacuo. Column chromatography separation purification (petroleum ether: ethyl acetate =200 = 1) yielded the product (iii) (1.6 g, 66.5%).
1 H NMR(600MHz,Chloroform-d)δ7.84(dd,J＝8.2,3.4Hz,2H),7.79(d,J＝7.9Hz,1H),7.61–7.57(m,2H),7.50–7.42(m,3H),5.89(dd,J＝5.5,2.6Hz,1H),4.21(dt,J＝6.1,2.1Hz,1H),3.49(dq,J＝4.9,2.4Hz,1H),1.87(d,J＝1.6Hz,3H),1.66(ddd,J＝11.7,8.8,2.9Hz,1H),1.14(dq,J＝9.9,6.5Hz,1H),1.07–1.03(m,1H),1.02(d,J＝6.5Hz,3H),0.94(dd,J＝6.8,3.6Hz,1H),0.86(d,J＝6.5Hz,3H).
The synthesis flow and the specific steps of the product (II) are as follows:
product (III) (0.66g, 2mmol) and K were weighed 2 CO 3 (0.3 g, 2.2mmol), 5ml of a methanol solution was added as a solvent, and the reaction was carried out at room temperature for 24 hours. After filtration, column chromatography separation and purification (petroleum ether: ethyl acetate = 250) gave the product (ii) (0.3 g, 68.1%).
1 H NMR(600MHz,Chloroform-d)δ7.27(dd,J＝6.3,1.8Hz,1H),5.82–5.77(m,1H),4.07(dt,J＝6.1,2.0Hz,1H),3.71(s,3H),3.37(dq,J＝5.0,2.3Hz,1H),1.80(d,J＝1.7Hz,3H),1.55(ddd,J＝11.6,8.7,2.8Hz,1H),1.20–1.12(m,1H),1.08(dp,J＝11.7,6.4Hz,1H),0.98(d,J＝6.5Hz,3H),0.93–0.85(m,1H),0.81(d,J＝6.5Hz,3H).
The synthesis process and specific steps of the raw material product A (I) are as follows:
product (ii) (0.3g, 1.36mmol) and NaOH (108mg, 2.72mmol) were weighed out, placed in a 6ml mixed solution of methanol and water (methanol: water =2 1), and reacted at 50 ℃ for 12h. After cooling to room temperature, 1N dilute hydrochloric acid (10 ml) was added, the mixture was extracted with dichloromethane, the organics combined, dried filtered and concentrated in vacuo to give crude product (I) as starting material A (0.26g, 92.3%).
Example 2
And (3) optimizing the synthesis of the raw material B:
the conventional synthesis of starting material B is a two-step reaction, as shown below. The product is synthesized by one step, and the reaction condition is optimized.
The optimized general reaction process comprises the following steps:
3, 5-dichloroaniline (1 eq), 4-methoxycarbonylphenylboronic acid (2.5 eq) and potassium phosphate (3 eq) were weighed into a round-bottomed flask, purged with a heat gun while introducing argon, cooled to room temperature, and then rapidly added with palladium acetate (2%) and Ruphos (5%) followed by argon for 15min. The oxygen-scavenging solvent was transferred to a round bottom flask and reacted at reflux temperature for 5h.
Raw materials: the cheaper 3, 5-dichloroaniline is selected, and the structure is as follows:
catalyst: two Ruphos screens were performed, ruphos-a [ 2-dicyclohexylphosphino-2 '- (N, N-dimethylamine) -biphenyl ] and Ruphos-b (2-dicyclohexylphos-2', 6 '-diisopropoxy-1, 1' -biphenyl), with the structures being respectively
Ruphos-a: the operation refers to a general reaction process, ruphos-a is used as a catalyst, all products obtained by the reaction are mono-substituted intermediate products, the structure is as follows, and target products are not obtained, so Ruphos-a is excluded.
1 H NMR(600MHz,Chloroform-d)δ8.11–8.05(m,2H),7.61–7.57(m,2H),6.97(t,J＝1.7Hz,1H),6.77(t,J＝1.8Hz,1H),6.69(t,J＝2.0Hz,1H),4.30(s,2H),3.94(s,3H).
Ruphos-b: the operation refers to a general reaction process, ruphos-b is used as a catalyst, and the target product is obtained by all reactions, and the structure is as follows, so Ruphos-b is selected as the catalyst.
1 H NMR(600MHz,Chloroform-d)δ8.10(d,J＝8.1Hz,4H),7.67(d,J＝8.1Hz,4H),7.23(t,J＝1.5Hz,1H),6.95(d,J＝1.5Hz,2H),3.94(s,6H),3.90(s,2H).
Solvent: three solvents were screened in total.
Solvent a-toluene and water: the operation refers to a general reaction process, ruphos-b is used as a catalyst, a reaction solvent is toluene and water, and the reflux temperature is 110 ℃. After the reaction is finished, thin Layer Chromatography (TLC) detection shows that all the products are intermediate products, so that the solvents of toluene and water are removed.
Solvent b-dioxane: the operation refers to a general reaction process, ruphos-b is used as a catalyst, a reaction solvent is dioxane, and the reflux temperature is 100 ℃. After the reaction is finished, a Thin Layer Chromatography (TLC) detection shows that an intermediate product is generated, so that dioxane as a solvent is removed.
Solvent b-anhydrous tetrahydrofuran: the operation refers to a general reaction process, ruphos-b is used as a catalyst, a reaction solvent is anhydrous tetrahydrofuran, and the reflux temperature is 75 ℃. After the reaction is finished, thin-layer chromatography (TLC) detection is carried out, and all target products are obtained, so that the solvent is selected to be anhydrous tetrahydrofuran.
To sum up: finally, the catalyst is Ruphos-b (2-dicyclohexyl phosphorus-2 ',6' -diisopropoxy-1, 1' -biphenyl), the solvent is anhydrous tetrahydrofuran, and the reflux temperature is 75 ℃.
The synthesis process and the specific steps of the raw material B are as follows:
3, 5-dichloroaniline (3.4g, 20mmol), 4-methoxycarbonylphenylboronic acid (9.5g, 52.8mmol) and potassium phosphate (15g, 70.7mmol) were weighed, charged into a 250ml round-bottom flask, purged with a heat gun while introducing argon, cooled to room temperature, and then rapidly added with palladium acetate (0.15g, 2%) and Ruphos (0.46g, 1mmol, 5%) and degassed with argon for 15min. 50ml of anhydrous tetrahydrofuran was transferred to a round bottom flask with a one-off syringe and refluxed at 75 ℃ for 5h. Cooling to room temperature, vacuum concentrating, removing most tetrahydrofuran solution, adding anhydrous ethanol in batches for dissolving, rapidly filtering, and collecting filter cake. Adding 20ml of dichloromethane and 50ml of water into the filter cake, adding a small amount of NaOH, stirring for 5min, pouring out the upper water phase, continuously adding 50ml of water, stirring, pouring out the water phase, and repeating for three times. The organic phase was collected by separation, and after adding methylene chloride to dissolve all solids, the mixture was filtered through celite and anhydrous magnesium sulfate, dried and concentrated in vacuo to obtain the product, i.e., raw material B (5.188g, 71.78%).
1 H NMR(600MHz,Chloroform-d)δ8.10(d,J＝8.1Hz,4H),7.67(d,J＝8.1Hz,4H),7.23(t,J＝1.5Hz,1H),6.95(d,J＝1.5Hz,2H),3.94(s,6H),3.90(s,2H). 13 C NMR(151MHz,Chloroform-d)δ166.96,147.35,145.54,141.92,130.04,129.08,127.09,116.91,113.59,52.15.
Example 3
The synthesis process and the specific steps of the novel V-type organic ligand are as follows:
A50-mL round-bottomed flask was charged with the starting material A (0.6g, 2.9mmol) and the starting material B (1.15g, 3.18mmol), and then with 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.67g, 3.49mmol), 1-hydroxybenzotriazole (0.47g, 3.48mmol) and N, N-diisopropylethylamine (0.94g, 7.27mmol), followed by addition of 8mL of DMF solvent and reaction at room temperature for 48 hours. Acidification with 5ml of dilute hydrochloric acid (1N) was added, extraction was performed with ethyl acetate, the organic phase was collected, dried, filtered and purified by column chromatography (petroleum ether: ethyl acetate =10: 1) to obtain the product, organic ligand (C), type V (1.25g, 78.1%).
1 H NMR(600MHz,Chloroform-d)δ8.08(d,J＝8.2Hz,4H),7.87(d,J＝1.5Hz,2H),7.83(s,1H),7.67(d,J＝8.2Hz,4H),7.54(d,J＝1.6Hz,1H),7.06(dd,J＝6.2,1.9Hz,1H),5.84(dt,J＝6.1,1.8Hz,1H),4.19(dt,J＝6.1,2.1Hz,1H),4.11(t,J＝7.1Hz,1H),3.92(s,6H),3.41(dd,J＝6.2,2.5Hz,1H),2.03(s,1H),1.84(d,J＝1.6Hz,3H),1.61(ddd,J＝11.6,8.7,2.9Hz,1H),1.02(d,J＝6.5Hz,3H),0.83(d,J＝6.5Hz,3H).
Example 4
Application of V-type organic ligand
2-cyclopentenone (41mg, 0.5 mmol) and phenylboronic acid (244mg, 2mmol) were charged into a Schlenck reaction tube equipped with a stirrer, the ligand (C) of catalyst type V obtained in example 3 (27mg, 10mol%) was added, and 2ml of a methanolic potassium hydroxide solution (2N) was added, followed by sealing and reacting at 80 ℃ for 12 hours. After completion of the reaction, it was cooled to room temperature, dissolved and diluted with ethyl acetate (20 mL), washed with a saturated aqueous potassium hydroxide solution (3 × 20 mL), and the organic phase was collected, dried, filtered, and concentrated in vacuo, and subjected to column chromatography separation and purification (petroleum ether: ethyl acetate =80 1) to obtain a product 1a (65mg, 81%,96% ee).
1 H NMR(600MHz,CDCl 3 )δ7.35(t,J＝7.6Hz,2H),7.26(t,J＝3.9Hz,3H),3.43(ddd,J＝22.1,11.1,6.9Hz,1H),2.67(dd,J＝18.2,7.5Hz,1H),2.51–2.41(m,2H),2.39–2.25(m,2H),2.05–1.95(m,1H).
Example 5
Application of V-type organic ligand
2-Cyclohexenone (48mg, 0.5 mmol) and phenylboronic acid (244mg, 2mmol) were charged into a Schlenck tube, and the catalyst type V ligand (C) (27mg, 10mol%) was added thereto, followed by addition of 2ml of KOH methanol solution (2N), sealing, and then reaction at 80 ℃ for 12 hours. After completion of the reaction, it was cooled to room temperature, dissolved and diluted with ethyl acetate (20 mL), washed with saturated aqueous KOH (3 × 20 mL), and the organic phase was collected, dried, filtered, and concentrated in vacuo, and subjected to column chromatography separation and purification (petroleum ether: ethyl acetate =80 1) to obtain a product 1b (72mg, 83%,95% ee).
1 H NMR(600MHz,CDCl 3 )δ＝7.33(t,J＝7.6,2H，),7.23(dd,J＝11.2,7.7,3H),3.01(ddd,J＝12.0,7.8,3.7,1H),2.63–2.57(m,1H),2.53(dd,J＝13.6,12.9,1H),2.46(dd,J＝14.3,1.5,1H),2.38(ddd,J＝19.6,13.5,6.2,1H),2.15(ddd,J＝13.2,6.3,3.2,1H),2.12–2.06(m,1H),1.83(ddd,J＝45.3,14.2,8.1,2H).
Example 6
Application of V-type organic ligand
To a Schlenck tube were added 5-methyl-3-ethen-2-one (60.6 mg,0.5 mmol) and phenylboronic acid (244mg, 2mmol), the catalyst type V ligand (C) (27mg, 10mol%), 2ml of KOH in methanol solution (2N) was added, and the mixture was sealed and reacted at 80 ℃ for 12 hours. After completion of the reaction, it was cooled to room temperature, dissolved and diluted with ethyl acetate (20 mL), washed with saturated aqueous KOH (3 × 20 mL), and the organic phase was collected, dried, filtered, and concentrated in vacuo, and purified by column chromatography (petroleum ether: ethyl acetate =80 1) to obtain a product 1c (76mg, 80%,90% ee).
1 H NMR(600MHz,CDCl 3 )δ7.29–7.24(m,2H),7.18(t,J＝7.4Hz,1H),7.14(d,J＝7.2Hz,2H),2.91(d,J＝6.0Hz,1H),2.79(dd,J＝7.2,4.5Hz,2H),1.97(s,3H),1.83(dd,J＝13.8,6.9Hz,1H),0.93(d,J＝6.7Hz,3H),0.74(d,J＝6.7Hz,3H).
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for synthesizing a V-type organic ligand is characterized by comprising the following steps: the method comprises the following steps: taking raw material A (1R, 4R, 7R) -7-isopropyl-5-methylbicyclo [2.2.2] octa-2, 5-diene-2-carboxylic acid and raw material B3, 5-di (4-methoxycarbonylphenyl) aniline as raw materials, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole and N, N-diisopropylethylamine as catalysts, and N, N-dimethylformamide as a solvent to react at room temperature for 48h, and purifying a reaction mixture to obtain a V-type organic ligand;
2. the method of synthesizing an organic ligand of type V according to claim 1, wherein: the catalyst content required for the reaction is as follows: the adding molar weight of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the 1-hydroxybenzotriazole is 1.2 times of that of the raw material A; the molar weight of the N, N-diisopropylethylamine is 2.5 times that of the raw material A.
3. The method of synthesizing an organic ligand of type V according to claim 1, wherein: the purification of the reaction mixture comprises the following steps: acidifying the reaction mixture by dilute hydrochloric acid, extracting by ethyl acetate, detecting by thin-layer chromatography, and purifying and separating by column chromatography to obtain the V-type organic ligand.
4. The method of synthesizing an organic ligand of type V according to claim 1, wherein: the synthesis method of the raw material A comprises the following steps:
(1) Taking propiolic acid and 2-naphthol as raw materials, 4-dimethylamino pyridine and dicyclohexyl carbodiimide as catalysts, taking dichloromethane as a solvent, adding materials in an ice bath, and reacting for 5 hours at room temperature to obtain 2-naphthyl propiolate shown in a formula IV;
(2) Taking the product shown in the formula IV and (R) -alpha-phellandrene as raw materials, taking dimethyl aluminum chloride as a catalyst and dichloromethane as a solvent, adding materials at-78 ℃, and reacting for 18 hours at room temperature to obtain a product shown in the formula III;
(3) Performing ester exchange on the product shown in the formula III, and reacting in a methanol solvent for 24 hours at room temperature under the catalysis of potassium carbonate to obtain a product shown in a formula II, wherein the product shown in the formula II is hydrolyzed to obtain a product shown in a formula I, namely a raw material A;
5. the method of synthesizing an organic ligand of type V according to claim 4, wherein: the amount of catalyst required during the synthesis of the product of formula IV is: adding 4-dimethylaminopyridine in a molar amount of 1% of that of 2-naphthol; the molar amount of dicyclohexylcarbodiimide was 1.1 times that of 2-naphthol.
6. The method of synthesizing an organic ligand of type V according to claim 4, wherein: the amount of catalyst required during the synthesis of the product of formula iii is: dimethyl aluminum chloride was added in a molar amount of 1.1 times that of the product represented by formula IV.
7. The method of synthesizing an organic ligand of type V according to claim 1, wherein: the synthesis method of the raw material B comprises the following steps: 3, 5-dichloroaniline and 4-methoxycarbonylphenylboronic acid are taken as raw materials, palladium acetate, potassium phosphate and Ruphos are taken as catalysts, anhydrous THF is taken as a solvent, and the raw materials B are obtained by refluxing for 5h at 75 ℃ under the anhydrous and anaerobic conditions;
8. the method of synthesizing an organic ligand of type V according to claim 7, wherein: the Ruphos is 2-dicyclohexyl phosphorus-2 ',6' -diisopropoxy-1, 1' -biphenyl, and the structural formula is as follows:
9. an organic ligand of type V synthesized using the synthesis method of any one of claims 1-8.
10. Use of a type V organic ligand synthesized by the synthesis method of any one of claims 1-8 as a catalyst to catalyze asymmetric addition reactions.
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