A porous organic polymer containing a chiral phosphorus-sulfur ligand and a preparation method and application thereof

Abstract

This invention provides a porous organic polymer containing chiral phosphorus-sulfur ligands, its preparation method, and its application. The method includes the following steps: adding a chiral phosphorus-sulfur ligand molecule of Formula I, divinylbenzene, styrene, and a polymerization initiator to a pore-forming solvent, performing a polymerization reaction at a temperature of 60–120°C, and removing the pore-forming solvent to obtain the porous organic polymer. R1 is a monosubstituted or polysubstituted group, each substituent selected from H, methoxy, vinyl, or vinylphenyl; R2 is a monosubstituted or polysubstituted group, each substituent selected from H, methoxy, vinyl, or vinylphenyl; R3 is selected from H, vinyl, or vinylphenyl; and at least one vinyl or vinylphenyl group is included in R1, R2, and R3. Based on the method of this invention, the problem of high cost and difficulty in recovering chiral phosphorus-sulfur ligands is addressed.

Description

Technical Field

[0001] This invention belongs to the field of polymer functional materials, specifically relating to a porous organic polymer containing chiral phosphorus-sulfur ligands, its preparation method, and its application. Background Technology

[0002] Chirality is one of the essential properties of nature. A large number of chiral molecules are found in nature and living organisms. Many biological macromolecules, such as proteins, polysaccharides and nucleic acids, which are the basis of life activities, are chiral. At the same time, chiral compounds also play an important role in pharmaceuticals, food science and chemical synthesis. Therefore, the efficient and selective synthesis of chiral compounds has become an important goal of scientists. Among them, the asymmetric synthesis of chiral compounds using chiral ligands and transition metal catalysis is the most direct and efficient way to obtain highly optically active compounds. As we all know, organophosphine ligands play an important role in asymmetric reactions, such as asymmetric allylation, asymmetric hydrogenation, and asymmetric hydroformylation [1]. The research group of Lu Liangqiu at Central China Normal University reported a series of novel chiral phosphorus-sulfur ligands that can typically prepare various chiral nitrogen and oxygen heterocyclic products with quaternary stereocenters and medium-sized rings in good yields and with high enantioselectivity in palladium-catalyzed asymmetric [4+2], [5+2], [6+2], and [8+2] dipolar cycloadditions and copper-catalyzed [3+2] cycloadditions. However, the reactions require the consumption of large amounts of chiral phosphorus-sulfur ligands, and the ligands are difficult to separate and recover from the reaction system, resulting in high costs. Summary of the Invention

[0003] The technical problem solved by this invention is to provide a porous organic polymer containing chiral phosphorus-sulfur ligands, its preparation method and application, so as to solve the problems of high recycling cost and difficulty in recycling chiral phosphorus-sulfur ligands.

[0004] The specific solution provided by this invention is as follows:

[0005] This invention provides a method for preparing a porous organic polymer containing a chiral phosphorus-sulfur ligand, comprising the following steps: adding a chiral phosphorus-sulfur ligand molecule of Formula I, divinylbenzene, styrene, and a polymerization initiator to a pore-forming solvent, performing a polymerization reaction at a temperature of 60–120°C, and removing the pore-forming solvent to obtain a porous organic polymer, wherein the pore-forming solvent is selected from one or more of tetrahydrofuran, toluene, or n-butanol;

[0006]

[0007] Wherein, R1 is a monosubstituted or polysubstituted group, each substituent being selected from H, methoxy, vinyl or vinylphenyl; R2 is a monosubstituted or polysubstituted group, each substituent being selected from H, methoxy, vinyl or vinylphenyl; R3 is selected from H, vinyl or vinylphenyl; and at least one vinyl or vinylphenyl group is included in R1, R2 and R3.

[0008] Based on the method of this invention, a porous organic polymer containing chiral phosphorus-sulfur ligands, divinylbenzene, and styrene is obtained by copolymerizing chiral phosphorus-sulfur ligands, resulting in a large specific surface area, well-developed pores, and a stable molecular framework. Its well-developed pore structure allows transition metals to readily complex with the chiral phosphorus-sulfur ligands and prevents dissociation from the ligands, thus improving catalyst stability. Its stable framework structure further stabilizes the chiral phosphorus-sulfur ligand structure, which helps maintain its chiral structure and prevents racemization when used as a ligand in catalytic reactions, thereby exhibiting high catalytic performance. Furthermore, the chiral phosphorus-sulfur ligand-divinylbenzene-styrene three-segment porous polymer material obtained by the method of this invention is easily separated and recovered from the solvent system, facilitating recycling.

[0009] Based on the above solution, the present invention can be further improved as follows:

[0010] Furthermore, the mass ratio of the chiral phosphorus sulfide ligand molecule, divinylbenzene, styrene, and polymerization initiator is 1:(0.1-0.2):(3-5):(0.1-0.3).

[0011] Furthermore, the pore-forming solvent is selected from one or more of tetrahydrofuran, toluene, or n-butanol.

[0012] Furthermore, the pore-forming solvent is a mixture of toluene and n-butanol, wherein the volume ratio of toluene to n-butanol in the mixture is 1:(4-6).

[0013] Furthermore, the polymerization initiator is azobisisobutyronitrile (AIBN).

[0014] Furthermore, the temperature is 70–100°C.

[0015] Furthermore, the chiral phosphorus-thioligand molecule is selected from one of the following structures:

[0016]

[0017] The present invention also provides porous organic polymers containing chiral phosphorus-sulfur ligands prepared by the method described above.

[0018] This invention also provides the application of the porous organic polymer containing chiral phosphorus-sulfur ligands as described above in palladium-catalyzed asymmetric dipole cycloaddition reactions.

[0019] Furthermore, it is applied to the palladium-catalyzed cycloaddition reaction of 4-vinylbenzoxazinone with α-diazoketone.

[0020] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0021] Figure 1 Compound 2 is a chiral phosphorus-sulfur ligand molecule. 1 H NMR spectrum.

[0022] Figure 2 Compound 2 is a chiral phosphorus-sulfur ligand molecule. 13 C NMR spectrum.

[0023] Figure 3 Compound 2 is a chiral phosphorus-sulfur ligand molecule. 31 P NMR spectrum.

[0024] Figure 4 For polymer II 13 1C MAS NMR plot.

[0025] Figure 5 For polymer II 31 P MAS NMR image.

[0026] Figure 6 This is the SEM image of polymer B.

[0027] Figure 7 This is a SEM image of polymer II.

[0028] Figure 8 This is a TEM image of polymer II. Detailed Implementation

[0029] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0030] This invention provides a method for preparing a porous organic polymer containing chiral phosphorus-sulfur ligands, comprising the following steps: adding the chiral phosphorus-sulfur ligand molecule shown in Formula I, divinylbenzene, styrene, and a polymerization initiator to a pore-forming solvent, and then performing a polymerization reaction at a temperature of 60–120°C to obtain a porous organic polymer;

[0031]

[0032] In this invention, R1 is a monosubstituted or polysubstituted group, each substituent selected from H, methoxy, vinyl, or vinylphenyl; R2 is a monosubstituted or polysubstituted group, each substituent selected from H, methoxy, vinyl, or vinylphenyl; R3 is selected from H, vinyl, or vinylphenyl; and at least one vinyl or vinylphenyl group is included in R1, R2, and R3. Based on the method of this invention, a porous organic polymer containing chiral phosphorus-sulfur ligands is copolymerized with chiral phosphorus-sulfur ligands, divinylbenzene, and styrene to obtain a polymer with a large specific surface area, well-developed pores, and a stable molecular skeleton. Its well-developed pore structure allows transition metals to smoothly complex with the chiral phosphorus-sulfur ligands and is less prone to dissociation from the ligands, thus improving the stability of the catalyst. Its stable skeleton structure makes the chiral phosphorus-sulfur ligand structure more stable, which helps maintain its chiral structure and prevents racemization when used as a ligand in catalytic reactions, thereby exhibiting high catalytic performance. Furthermore, the chiral phosphorus-sulfur ligand-divinylbenzene-styrene three-segment porous polymer material obtained by the method of this invention is easily separated and recovered from the solvent system, facilitating recycling.

[0033] The method for preparing a porous organic polymer containing chiral phosphorus-sulfur ligands according to embodiments of the present invention, wherein the mass ratio of the chiral phosphorus-sulfur ligand molecules, divinylbenzene, vinylbenzene, and polymerization initiator is 1:(0.1-0.2):(3-5):(0.1-0.3). Using the chiral phosphorus-sulfur ligand molecules and styrene as the main monomer raw materials, supplemented with an appropriate amount of divinylbenzene monomer, a porous polymer with stable performance and high catalytic activity can be obtained.

[0034] Specifically, the divinylbenzene is selected from one or more of o-divinylbenzene, m-divinylbenzene, or p-divinylbenzene.

[0035] The method for preparing porous organic polymers containing chiral phosphorus-sulfur ligands based on embodiments of the present invention uses a pore-forming solvent selected from one or more of tetrahydrofuran, toluene, or n-butanol.

[0036] The method for preparing a porous organic polymer containing chiral phosphorus-sulfur ligands according to embodiments of the present invention uses a pore-forming solvent that is a mixture of toluene and n-butanol, wherein the volume ratio of toluene to n-butanol in the mixture is 1:(4-6). At this solvent ratio, after the pore-forming solvent is removed, a porous polymer with uniform pore size and high porosity can be formed.

[0037] The method for preparing porous organic polymers containing chiral phosphorus and sulfur ligands based on embodiments of the present invention uses azobisisobutyronitrile as the polymerization initiator.

[0038] The method for preparing porous organic polymers containing chiral phosphorus-sulfur ligands based on embodiments of the present invention, wherein the temperature is 70–100°C.

[0039] The method for preparing porous organic polymers containing chiral phosphorus-sulfur ligands based on embodiments of the present invention, wherein the chiral phosphorus-sulfur ligand molecule is selected from one of the following structures:

[0040]

[0041] Correspondingly, the structure of porous organic polymers containing chiral phosphorus-sulfur ligands is shown below:

[0042]

[0043] Example 1

[0044] Preparation of polymer I: 0.2 mmol (143 mg) of compound 1, 0.2 mmol (26 mg) of p-divinylbenzene, 831 mg of styrene and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C and reacted for 24 h. The solvent was removed by distillation and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer I.

[0045] Example 2

[0046] Preparation of Polymer II: 0.2 mmol (148 mg) of Compound 2, 0.2 mmol (26 mg) of p-divinylbenzene, 826 mg of styrene, and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white Polymer II. Figure 1 For compound 2 1 H NMR spectrum, Figure 2 For compound 2 13 C NMR spectrum, Figure 3 For compound 2 31 p NMR spectrum, Figure 4 For polymer II 13 1C MAS NMR spectrum Figure 5 For polymer II 31 pMAS NMR plot.

[0047] Example 3

[0048] Preparation of Polymer III: 0.2 mmol (154 mg) of Compound 3, 0.2 mmol (26 mg) of p-divinylbenzene, 820 mg of styrene and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C and reacted for 24 h. The solvent was removed by distillation and the mixture was dried under vacuum at 60 °C for 12 h to obtain white Polymer III.

[0049] Example 4

[0050] Preparation of polymer IV: 0.2 mmol (161 mg) of compound 4, 0.2 mmol (26 mg) of p-divinylbenzene, 813 mg of styrene and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C and reacted for 24 h. The solvent was removed by distillation and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer IV.

[0051] Example 5

[0052] Preparation of polymer V: 0.2 mmol (166 mg) of compound 5, 0.2 mmol (26 mg) of p-divinylbenzene, 808 mg of styrene and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C and reacted for 24 h. The solvent was removed by distillation and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer V.

[0053] Example 6

[0054] Preparation of polymer VI: 0.2 mmol (182 mg) of compound 6, 0.2 mmol (26 mg) of p-divinylbenzene, 792 mg of styrene and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C and reacted for 24 h. The solvent was removed by distillation and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer VI.

[0055] Example 7

[0056] Preparation of polymer VII: 0.2 mmol (184 mg) of compound 7, 0.2 mmol (26 mg) of p-divinylbenzene, 790 mg of styrene and 15 mg of azobisisobutyronitrile were dissolved in 6 mL of a mixed solvent of n-octanol and toluene in a volume ratio of 5:1. The mixture was stirred and heated to 70 °C and reacted for 24 h. The solvent was removed by distillation and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer VII.

[0057] Comparative Example 1

[0058] Preparation of Polymer A: 0.2 mmol (143 mg) of Compound 1, 857 mg of p-divinylbenzene, and 25 mg of azobisisobutyronitrile were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white Polymer A. The specific surface area of ​​the obtained polymer was 535 m². 2 Approximately / g.

[0059] Comparative Example 2

[0060] Preparation of Polymer B: 0.2 mmol (148 mg) of Compound 2, 852 mg of p-dienylbenzene, and 25 mg of azobisisobutyronitrile were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer B. N2 adsorption results showed that the specific surface area of ​​the obtained polymer was 635 m² / g. 2 Approximately / g.

[0061] Comparative Example 3

[0062] Preparation of Polymer C: 0.2 mmol (154 mg) of Compound 3, 846 mg of p-dienylbenzene, and 25 mg of azobisisobutyronitrile were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white Polymer C. N2 adsorption results showed that the specific surface area of ​​the obtained polymer was 518 m². 2 Approximately / g.

[0063] Comparative Example 4

[0064] Preparation of Polymer D: 0.2 mmol (161 mg) of Compound 4, 839 mg (p-dienylbenzene), and 25 mg (azobisisobutyronitrile) were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white Polymer D. The specific surface area of ​​the obtained polymer was 489 m². 2 Approximately / g.

[0065] Comparative Example 5

[0066] Preparation of polymer D: 0.2 mmol (166 mg) of compound 5, 834 mg (p-dienylbenzene), and 25 mg (azobisisobutyronitrile) were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain a white polymer E. The specific surface area of ​​the obtained polymer was 505 m². 2 Approximately / g.

[0067] Comparative Example 6

[0068] Preparation of polymer F: 0.2 mmol (182 mg) of compound 6, 821 mg (p-dienylbenzene), and 25 mg (azobisisobutyronitrile) were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer F. N2 adsorption results showed that the specific surface area of ​​the obtained polymer was 469 m². 2Approximately / g.

[0069] Comparative Example 7

[0070] Preparation of Polymer G: 0.2 mmol (184 mg) of compound 6, 816 mg (p-dienylbenzene), and 25 mg (azobisisobutyronitrile) were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred and heated to 100 °C for 24 h. The solvent was removed by distillation, and the mixture was dried under vacuum at 60 °C for 12 h to obtain white polymer G. N2 adsorption results showed that the specific surface area of ​​the obtained polymer was 510 m² / g. 2 Approximately / g.

[0071] Comparative Example 8

[0072] Similar to Example 1, except that no styrene was added in the preparation of polymer I, only 857 mg of divinylbenzene was added.

[0073] Comparative Example 9

[0074] Similar to Example 1, except that no styrene was added in the preparation of polymer I, only 857 mg of styrene was added.

[0075] Specifically, the preparation methods of chiral phosphorus-sulfur ligand molecular compounds 1, 3, 5, and 7 are as follows: 3 mmol of precursor compound 12 is dissolved in 15 mL of toluene solution. 3 mmol of phosphorus trichloride and 3.3 mmol of triethylamine are added at 0 °C. After reacting at 70 °C for 7 h, the mixture is cooled to room temperature. 6 mmol of a phenolic compound and 9.9 mmol of triethylamine are added to the reaction system under ice bath conditions. The mixture is stirred at room temperature for 12 h to obtain the chiral phosphorus-sulfur ligand molecular compounds. Specifically, when the phenolic compound is phenol, chiral phosphorus-sulfur ligand molecular compound 1 is obtained; when the phenolic compound is p-vinylphenol, chiral phosphorus-sulfur ligand molecular compound 3 is obtained; when the phenolic compound is 4-methoxy-2-vinylphenol, chiral phosphorus-sulfur ligand molecular compound 5 is obtained; and when the phenolic compound is 4′-vinyl(1,1′-biphenyl)-4-phenol, chiral phosphorus-sulfur ligand molecular compound 7 is obtained.

[0076] Specifically, the preparation methods for chiral phosphorus-sulfur ligand molecular compounds 2, 4, and 6 are as follows: 3 mmol of compound 11 is dissolved in 15 mL of toluene solution. 3 mmol of phosphorus trichloride and 3.3 mmol of triethylamine are added at 0 °C. After reacting at 70 °C for 7 h, the mixture is cooled to room temperature. 6 mmol of a phenolic compound and 9.9 mmol of triethylamine are added to the reaction system under ice bath conditions. The mixture is stirred at room temperature for 12 h to obtain the chiral phosphorus-sulfur ligand molecular compounds. Specifically, when the phenolic compound is p-vinylphenol, chiral phosphorus-sulfur ligand molecular compound 2 is obtained; when the phenolic compound is 4-methoxy-2-vinylphenol, chiral phosphorus-sulfur ligand molecular compound 4 is obtained; and when the phenolic compound is 4′-vinyl(1,1′-biphenyl)-4-phenol, chiral phosphorus-sulfur ligand molecular compound 6 is obtained.

[0077]

[0078] I. Characterization Test

[0079] Polymer B prepared in Comparative Example 2 and polymer I1 prepared in Example 2 were characterized by SEM, and the SEM images are shown below. Figure 6 and Figure 7 As shown, the polymer II powder sample prepared in Example 2 was subjected to TEM verification, and the results are as follows. Figure 8 As shown in the figure, the characterization results indicate that the polymer II prepared in Example 2 has a rich pore structure.

[0080] II. Application of Polymers in Palladium-Catalyzed Cycloaddition of 4-Vinylbenzoxazinone 13 to α-Diazone 14

[0081] Compound 1, along with the products obtained in Examples 1-7 and Comparative Examples 1-9, were used as ligands to coordinate with palladium and could undergo a [4+2] dipolar cycloaddition reaction. The reaction substrates were 4-vinylbenzoxazinone 13 and α-diazotone 14. The specific experimental procedure was as follows: In a 10 mL Schlenk tube filled with argon and dried, Pd2(dba)3·CHCl3 (0.005 mmol, 5 mol%) and a chiral phosphorus-sulfur ligand polymer (0.011 mmol, 11 mol%) were placed in 1.0 mL of DCM and stirred at room temperature for 30 min. Vinylbenzoxazinone (0.1 mmol, 33 mg) and α-diazotone (0.2 mmol, 32 mg) dissolved in 0.5 mL of DCM were added, and the mixture was placed under 6 W blue LEDs and reacted at room temperature for 24 hours.

[0082]

[0083] In the palladium-catalyzed reaction of 4-vinylbenzoxazinone 13 with α-diazotone 14, different products participated in the reaction as ligands, and the corresponding yields and enantioselectivity are shown in Table 1.

[0084] Table 1. Ligands and their corresponding yields and selectivity in the palladium-catalyzed cycloaddition of 4-vinylbenzoxazinone 13 to α-diazotone 14

[0085]

[0086]

[0087] The above experiments show that although copolymerization of divinylbenzene and chiral phosphorus-sulfur ligands can yield two-segment porous polymer materials with large specific surface areas, most of the polymerized two-segment porous polymers (such as polymers B, C, F, G, and the polymers prepared in Comparative Examples 8 and 9) essentially lose their activity compared to the chiral phosphorus-sulfur ligand compounds that possess coordination catalytic activity. Compared to two-segment porous polymer materials used as ligands (polymers A, D, and G), three-segment porous polymer materials formed by copolymerizing divinylbenzene, vinylbenzene, and chiral phosphorus-sulfur ligands using chiral phosphorus-sulfur ligands, vinylbenzene, and divinylbenzene as monomer raw materials show significantly improved coordination catalytic yields, reaching up to 99%, and enantioselectivity reaching 92%. Based on the method of this invention, the structure of chiral phosphorus-sulfur ligands can be made more stable and less prone to racemization, thus maximizing the smooth complexation of transition metals with chiral phosphorus-sulfur ligands, ensuring the catalytic activity of the catalyst, and thereby obtaining higher catalytic yields.

[0088] III. Recycling Experiment

[0089] In the palladium-catalyzed cycloaddition of 4-vinylbenzoxazinone 13 to α-diazotone 14, recovery experiments were conducted using polymer VI and polymer A as ligands, and the changes in yield and enantioselectivity are shown in Tables 2 and 3.

[0090] Table 2. Number of recoveries of ligand polymer VI and their corresponding yields and enantioselectivity

[0091]

[0092]

[0093] Table 3. Number of recoveries of ligand polymer A and their corresponding yields and enantioselectivity

[0094]

[0095] Based on polymer VI of the present invention, after five recycling cycles, the yield remains as high as 99%, with an enantioselectivity of 92%, both of which are superior to polymer A. The three-segment porous polymer material prepared by the method of the present invention has a stable framework structure, which makes the chiral phosphorus-sulfur ligand structure more stable, thereby ensuring the stability of the catalyst's catalytic activity and increasing the number of recycling cycles.

[0096] Although embodiments of the present invention have been described in detail above, those skilled in the art will understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A method for preparing a porous organic polymer containing chiral phosphorus-sulfur ligands, characterized in that, Includes the following steps: Chiral phosphorus-sulfur ligand molecules, divinylbenzene, styrene and polymerization initiator shown in Formula I are added to a pore-forming solvent and polymerized at a temperature of 60-120°C. After removing the pore-forming solvent, a porous organic polymer is obtained. Wherein, R1 is a monosubstituted or polysubstituted group, each substituent being selected from H, methoxy, vinyl or vinylphenyl; R2 is a monosubstituted or polysubstituted group, each substituent being selected from H, methoxy, vinyl or vinylphenyl; R3 is selected from H, vinyl or vinylphenyl; and at least one vinyl or vinylphenyl group is included in R1, R2 and R3.

2. The method for preparing the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 1, characterized in that, The mass ratio of the chiral phosphorus sulfide ligand molecule, divinylbenzene, styrene, and polymerization initiator is 1:(0.1-0.2):(3-5):(0.1-0.3).

3. The method for preparing the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 1, characterized in that, The pore-forming solvent is selected from one or more of tetrahydrofuran, toluene, or n-octanol.

4. The method for preparing the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 3, characterized in that, The pore-forming solvent is a mixture of toluene and n-octanol, wherein the volume ratio of toluene to n-octanol in the mixture is 1:(4-6).

5. The method for preparing the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 1, characterized in that, The polymerization initiator is azobisisobutyronitrile.

6. The method for preparing the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 1, characterized in that, The temperature is 70–100°C.

7. The method for preparing the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 1, characterized in that, The chiral phosphorus-thionyl ligand molecule is selected from one of the following structures: 。 8. A porous organic polymer containing chiral phosphorus-sulfur ligands, characterized in that, It is prepared by the method described in any one of claims 1-7.

9. The application of the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 8, characterized in that, It is applied to palladium-catalyzed asymmetric dipole cycloaddition reactions.

10. The application of the porous organic polymer containing chiral phosphorus-sulfur ligands according to claim 9, characterized in that, It is applied to the palladium-catalyzed cycloaddition reaction of 4-vinylbenzoxazinone with α-diazoketone.

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