A method for selective arylation of o-carborane B(6)-H

Abstract

The present invention designs a method for the selective arylation of o-carborane B(6)-H, which belongs to the field of organic synthetic chemistry. Using B(3)-aryl-o-carborane as a raw material, Cp*IrCl2 catalyzes the selective activation of B(6)-H as an entry point, in the presence of a catalyst and an additive, the selective oxidative coupling of arylboronic acid and B(6)-H is achieved in tetrahydrofuran by room temperature reaction for 24 hours, and a series of B(3,6)-diaryl-o-carborane derivatives are synthesized. The substrate involved in the present invention has the advantages of good functional group compatibility, mild reaction conditions, and high regioselectivity. The present invention provides a simple and efficient synthesis method for the synthesis of diaryl-o-carborane derivatives, laying a technical foundation for their application in the fields of medicinal chemistry and materials science.

Description

Technical Field

[0001] The invention belongs to the field of organic synthetic chemistry, and particularly relates to a method for selective arylation of o-carborane B(6)-H. Background Art

[0002] Due to their unique spatial structure and electronic properties, icosahedral o-carboranes have high boron content and excellent thermal and chemical stability. They have been widely used in medicinal chemistry, materials science, organometallic chemistry, and coordination chemistry, and have shown great application prospects in boron neutron capture therapy (BNCT). Therefore, the development of functionalization methods for o-carboranes and the diversified synthesis of their derivatives has become an important research direction in carborane chemistry.

[0003] In recent years, the use of electrophilic BH activation and directing group-guided BH activation strategies based on differences in BH bond charge density has greatly promoted the rapid development of B(8,9,10,12)-H and B(4,5)-H selective functionalization. However, the electron-deficient B(3,6)-H bond has the lowest charge density and is difficult to undergo electrophilic reactions, making its selective activation still a difficult problem to be solved.

[0004] In 1988, the Sneddon group used Cp*IrCl to catalyze the activation of B(3)-H for the first time to realize its hydroboration reaction with alkynes. However, this reaction was only applicable to propyne and the yield was low. In 2017, Professor Xie Zuowei and Professor Qiu Zaozao used [(cod)IrCl]2 to catalyze the activation of BH to realize the selective borylation reaction of B(3,6)-H. However, the reaction efficiency of Bpin-o-carborane in the conversion to Ar-o-carborane was not ideal. In 2019, our group achieved the selective activation of o-carborane B(3,6)-H and its coupling with iodoaryl hydrocarbons through the electron-rich catalytic system generated in situ by Pd-NHC. However, there is still a lack of sufficient understanding of the basic rules for the selective activation / functionalization of electron-deficient B(3,6)-H. Based on this, this patent uses arylboronic acid as a coupling unit to carry out research on the selective arylation of o-carborane B(6)-H.

[0005] This patent uses the selective activation of B(6)-H as the starting point and arylboronic acid as the source of aryl groups to achieve the selective arylation of o-carborane B(6)-H under mild conditions, thereby obtaining a series of B(3,6)-diaryl-o-carborane derivatives. This method provides an economical and efficient method for the selective functionalization of the BH bond of o-carborane, lays a theoretical and technical foundation for further design of the selective functionalization of o-carborane B(6)-H, and provides a material basis for exploring the application of B(3,6)-diaryl-o-carborane derivatives in related disciplines. Summary of the Invention

[0006] Based on the important application value of o-carborane derivatives in the fields of medicinal chemistry and materials science, the purpose of the present invention is to provide a method for the selective arylation of B(6)-H with simple operation, mild synthesis conditions and wide applicability.

[0007] In order to achieve the above-mentioned object of the invention, the synthetic route of the present invention is as follows:

[0008]

[0009] Among them, ●=C,○=B, and other vertices=BH

[0010] The method uses B(3)-aryl-o-carborane and aryl boronic acid as raw materials and comprises the following steps:

[0011] B(3)-aryl-o-carborane and arylboronic acid are used as raw materials, and in the presence of a catalyst and an additive, a cross-coupling reaction occurs in a solvent to generate B(3,6)-diaryl-o-carborane derivatives.

[0012] Wherein R is selected from hydrogen, phenyl, substituted phenyl, and the substituent in the substituted phenyl is methyl, ethyl, phenyl, tert-butyl, naphthyl, methoxy, ester, trifluoromethyl, or halogen.

[0013] Furthermore, in the above technical solution, the organic solvent is tetrahydrofuran.

[0014] Furthermore, in the above technical solution, the catalyst is dichloro(pentamethylcyclopentadienyl)iridium dimer, the additives are cesium fluoride, silver hexafluoroantimonate, silver tetrafluoroborate and a trace amount of deionized water; the molar ratio of B(3)-aryl-o-carborane to aryl boronic acid reagent is 1:1~5, the molar ratio of B(3)-aryl-o-carborane to catalyst is 50~100:1, and the molar ratio of B(3)-aryl-o-carborane to additive is 1:1~5.

[0015] Furthermore, in the above technical solution, the temperature is 25-80°C.

[0016] Furthermore, in the above technical solution, the reaction is carried out in air without the need for inert gas protection.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] 1. The present invention does not use a directing group, but only utilizes the electronic effect of o-carborane to regulate the selective arylation of B(6)-H.

[0019] 2. The reaction conditions of the present invention are mild and can be reacted under room temperature, anhydrous oxygen sensitivity and other stringent requirements.

[0020] 3. The reactants involved in the present invention have good universality and are suitable for a variety of substituents including methyl, ethyl, phenyl, tert-butyl, naphthyl, methoxy, ester, trifluoromethyl, and halogen.

[0021] 4. The reaction involved in the present invention has good selectivity and high yield, a simple reaction system and simple post-processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 1. Figure 1 is 3a in Example 1 of the present invention 1 HNMR;

[0023] 2. Figure 2 is 3a in Example 1 of the present invention 13 C NMR;

[0024] 3. Figure 3 is 3b in Example 2 of the present invention 1 HNMR;

[0025] 4. Figure 4 is 3b in Example 2 of the present invention 13 C NMR;

[0026] 5. Figure 5 is 3c in Example 3 of the present invention 1 HNMR;

[0027] 6. Figure 6 is 3c in Example 3 of the present invention 13 C NMR;

[0028] 7. Figure 7 is 3d in Example 4 of the present invention 1 HNMR;

[0029] 8. Figure 8 is 3d in Example 4 of the present invention 13 C NMR;

[0030] 9. Figure 9 is 3e in Example 5 of the present invention1 HNMR;

[0031] 10. Figure 10 is 3e in Example 5 of the present invention 13 C NMR;

[0032] 11. Figure 11 is 3f in Example 6 of the present invention 1 HNMR;

[0033] 12. Figure 12 is 3f in Example 6 of the present invention 13 C NMR;

[0034] 13. Figure 13 3g of Example 7 of the present invention 1 HNMR;

[0035] 14. Figure 14 3g of Example 7 of the present invention 13 C NMR;

[0036] 15. Figure 15 is 3h in Example 8 of the present invention 1 HNMR;

[0037] 16. Figure 16 is 3h in Example 8 of the present invention 13 C NMR;

[0038] 17. Figure 17 is 3i in Example 9 of the present invention 1 HNMR;

[0039] 18. Figure 18 is 3i in Example 9 of the present invention 13 C NMR;

[0040] 19. Figure 19 is 3k in Example 11 of the present invention 1 HNMR;

[0041] 20. Figure 20 is 3k in Example 11 of the present invention 13 C NMR;

[0042] twenty one. Figure 21 is 31 in Example 12 of the present invention 1 HNMR;

[0043] twenty two. Figure 22 is 31 in Example 12 of the present invention 13 C NMR;

[0044] twenty three. Figure 23 3m in Example 13 of the present invention 1 HNMR;

[0045] twenty four. Figure 24 is 3m in Example 13 of the present invention 13 C NMR;

[0046] 25. Figure 25 is 3n in Example 14 of the present invention 1 HNMR;

[0047] 26. Figure 26 is 3n in Example 14 of the present invention 13 C NMR;

[0048] 27. Figure 27 is 3o in Example 15 of the present invention 1 HNMR;

[0049] 28. Figure 28 is 3o in Example 15 of the present invention 13 C NMR;

[0050] 29. Figure 29 is 3p in Example 16 of the present invention 1 HNMR;

[0051] 30. Figure 30 is 3p in Example 16 of the present invention 13 C NMR;

[0052] 31. Figure 31 is 5a in Example 20 of the present invention 1 HNMR;

[0053] 32. Figure 32 is 5a in Example 20 of the present invention 13 C NMR;

[0054] 33. Figure 33 is 5b in Example 21 of the present invention 1 HNMR;

[0055] 34. Figure 34 is 5b in Example 21 of the present invention 13 C NMR;

[0056] 35. Figure 35 is 5c in Example 22 of the present invention 1 HNMR;

[0057] 36. Figure 36 is 5c in Example 22 of the present invention 13 C NMR;

[0058] 37. Figure 37 is 5d in Example 23 of the present invention 1 HNMR;

[0059] 38. Figure 38 is 5d in Example 23 of the present invention 13 C NMR;

[0060] 39. Figure 39 is 5e in Example 21 of the present invention 1 HNMR;

[0061] 40. Figure 40 is 5e in Example 21 of the present invention 13 C NMR;

[0062] 41. Figure 41 is 5f in Example 22 of the present invention 1 HNMR;

[0063] 42. Figure 42 is 5f in Example 22 of the present invention 13 C NMR;

[0064] 43. Figure 43 5g of Example 23 of the present invention 1 HNMR;

[0065] 44. Figure 44 5g of Example 23 of the present invention 13 C NMR;

[0066] 45. Figure 45 is 5h in Example 23 of the present invention 1 HNMR;

[0067] 46. Figure 46 is 5h in Example 23 of the present invention 13 C NMR. DETAILED DESCRIPTION

[0068] The present invention is further described in detail below with reference to a specific implementation case. This implementation case is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following implementation case.

[0069] Condition optimization:

[0070] Using B(3)-aryl-o-carborane and arylboronic acid as raw materials, a cross-coupling reaction occurs in a solvent in the presence of a catalyst and additives to produce B(3,6)-diaryl-o-carborane derivatives. The specific reaction conditions are optimized as follows:

[0071]

[0072]

[0073]

[0074] Taking the synthesis of B(3,6)-diphenyl-o-carborane (3a) from B(3)-phenyl-o-carborane (1a) and phenylboronic acid (2a) as an example, the reaction conditions were optimized by changing the reaction solvent, catalyst, silver salt, additives, etc. as follows:

[0075] After condition screening, the optimal condition for the synthesis of (3a) was screened out as No. 16: using B(3)-phenyl-o-carborane 1a (0.1mmol, 22mg) and phenylboronic acid (0.4mmol, 48mg) as model substrates, Cp*IrCl2 (10mol%, 8mg) as catalyst, AgBF4 (4eq, 80mg) and AgSbF6 (1eq, 34mg) as oxidants, CsF (3eq, 45mg) as base, in 1mL THF with a trace amount of H2O (4eq, 20μl), the reaction was carried out at room temperature for 24h, and compound 3a could obtain the best yield of 83%.

[0076] Substrate expansion:

[0077] According to the above optimized reaction conditions, after replacing other reaction substrates, the results are as follows:

[0078]

[0079] Implementation Case 1

[0080]

[0081] To a 10 ml reaction flask were added compound 1a (22 mg, 0.1 mmol), compound 2a (48 mg, 0.4 mmol), THF (1 ml), dichloro(pentamethylcyclopentadienyl)iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol), and water (7.2 mg, 0.4 mmol). The mixture was reacted in air at room temperature for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction. The inorganic salts were removed by filtration through a short silica gel column, and the mixture was concentrated under reduced pressure and separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 24.2 mg of product 3a in an 82% yield. 1HNMR (500MHz, CDCl3, ppm): δ7.63-7.61 (d, 4H, J = 10Hz), 7.44-7.40 (m, 2H), 7.38-7.35 (m, 4H), 3.85 (s, 2H, Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ132.3,

[0082] 128.9,127.4,58.2; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.2(2B),-3.8[2B,B(3,6)-Ph],

[0083] -11.3(2B),-12.9(4B); HRMS:calculated for C 14 B 10 H 19 - (MH) - 297.24228,found297.24203.

[0084] Implementation Case 2

[0085]

[0086] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction bottle, compound 1a (22 mg, 0.1 mmol), compound 2b (54 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air conditions for 24 h. After the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the mixture was separated by column chromatography with petroleum ether: ethyl acetate.

[0087] (20:1) was used as the eluent to obtain 15.8 mg of product 3b with a yield of 51%. 1H NMR (500MHz, CDCl3, ppm): δ7.62-7.61 (d, 2H, J = 5Hz), 7.51-7.50 (d, 2H, J = 5Hz), 7.43-7.40(m,1H),7.38-7.35(m,2H),7.19-7.18(d,2H,J=5Hz),3.83(s,2H,Cage CH),2.36(s,3H,-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ139.9,133.2,129.8,129.1,128.3,59.1,29.7,21.4; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-3.7[2B,B(3)-Ph&B(6)-Ph],-11.4(2B),-13.0(4B); HRMS: calculated for C 15 H 22 B 10 - (MH) - 311.2579, found 311.2584.

[0088] Implementation Case 3

[0089]

[0090] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 2c (75 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3c was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 22.0 mg of product 3c in a 68% yield. 1H NMR (500MHz, CDCl3, ppm): δ7.62-7.61 (d, 2H, J = 5Hz), 7.54-7.53 (d, 2H, J = 6Hz), 7.43-7.40(m,1H),7.37-7.35(m,2H),7.21-7.20(d,2H,J=5Hz),3.83(s,2H,Cage CH),2.67-2.64(q,2H,J=5Hz,-CH2-),1.24(t,3H,J=5Hz,-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ146.2,133.3,133.2,129.8,128.3,127.9,59.1,29.7,28.8,15.5; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-3.7[2B,B(3)-Ph&B(6)-Ph],-11.4(2B),-13.0(4B); HRMS: calculated for C 16 H 24 B 10 - (MH) - 325.2735,found 311.2748.

[0091] Implementation Case 4

[0092]

[0093] According to the method of Example 1, the reaction conditions are as follows: to a 10ml reaction flask, compound 1a (22mg, 0.1mmol), compound 2d (72mg, 0.4mmol), THF 1ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8mg, 0.01mmol), silver hexafluoroantimonate (25mg, 0.1mmol), silver tetrafluoroborate (80mg, 0.4mmol), cesium fluoride (45mg, 0.3mmol) and water (7.2mg, 0.4mmol) were added in sequence and reacted at room temperature under air conditions for 24h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3d was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as eluent to obtain 27.5mg of product 3d with a yield of 65%. 1H NMR (500MHz, CDCl3, ppm): δ7.61-7.60 (d, 2H, J = 5Hz), 7.57-7.55 (d, 2H, J = 10Hz), 7.43-7.39 (m, 3H), 7.38-7.35 (m, 2H), 3.84 (s, 2H, Cage CH),1.32(s,9H,-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ153.1,133.2,133.1,128.3,125.3,59.2,34.7,31.2,29.8,29.7,22.7,14.2; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-3.7[2B,B(3)-Ph&B(6)-Ph],-11.4(2B),-13.0(4B); HRMS: calculated forC 18 H 28 B 10 - (MH) - 353.3048,found 353.3040.

[0094] Implementation Case 5

[0095]

[0096] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 2e (61 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3e was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 12.5 mg of the product 3e in a 38% yield. 1H NMR (500MHz, CDCl3, ppm): δ7.62-7.61 (d, 2H, J = 5Hz), 7.55-7.53 (d, 2H, J = 5Hz), 7 .42(t,1H,J=5Hz),7.36(t,2H,J=10Hz),7.39-7.36(m,3H),3.82(m,5H,CH3&Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ161.1,134.6,133.2,129.8,128.3,113.9,59.2,55.3,31.7,29.7,22.7,14.2; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.2(2B),-3.3[2B,B(3)-Ph&B(6)-Ph],-11.2(2B),-12.8(4B); HRMS: calculated for C20H24B10-(MH)-373.2735, found 373.2747.

[0097] Implementation Case 6

[0098]

[0099] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction bottle, compound 1a (22 mg, 0.1 mmol), compound 2f (80 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air conditions for 24 h. After the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3f was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 26.9 mg of the product 3f with a yield of 72%. 1 H NMR (500MHz, CDCl3, ppm): δ7.70-7.69 (d, 2H, J = 5Hz), 7.64-7.63 (d, 2H, J = 5H) z),7.61-7.58(m,4H),7.47-7.41(m,3H),7.39-7.36(m,3H),3.89(s,2H,Cage CH),; 13 C{ 1H}NMR (125MHz, CDCl3, ppm): δ142.7,140.5,133.7,133.2,129.9,128.9,128.3,127.8,127.2,127.0,59.1,29.7,1.1; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.2(2B),-3.8[2B,B(3)-Ph&B(6)-Ph],-11.3(2B),-13.0(4B); HRMS: calculated for C 20 H 24 B 10 - (MH) - 373.2735, found 373.2747.

[0100] Implementation Case 7

[0101]

[0102] According to the method of Example 1, the reaction conditions are as follows: to a 10ml reaction flask, compound 1a (22mg, 0.1mmol), compound 2g (68mg, 0.4mmol), THF 1ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8mg, 0.01mmol), silver hexafluoroantimonate (25mg, 0.1mmol), silver tetrafluoroborate (80mg, 0.4mmol), cesium fluoride (45mg, 0.3mmol) and water (7.2mg, 0.4mmol) were added in sequence and reacted at room temperature under air conditions for 24h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 3g 26.0mg, with a yield of 75%. 1 H NMR (500MHz, CDCl3, ppm): δ8.11(s,1H),7.86-7.83(m,3H),7.68-7.64(m,3H) ),7.53-7.50(m,2H),7.45-7.42(m,1H),7.39-7.36(m,2H),3.95(s,2H,Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ133.9,133.8,133.2,129.9,129.4,128.4,127.0,126.6,59.2,32.0,29.7,22.7,14.2; 11 B{1 H}NMR (160MHz, CDCl3, ppm): δ-2.1(2B),-3.6[2B,B(3)-Ph&B(6)-Ph],-11.2(2B),-12.8(4B).

[0103] Implementation Case 8

[0104]

[0105] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction bottle, compound 1a (22 mg, 0.1 mmol), compound 2h (54 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air conditions for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3h was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 19.9 mg of the product 3h with a yield of 64%. 1 H NMR (500 MHz, CDCl 3 ,ppm): δ7.63-7.62(d,2H,J=5Hz),7.44-7.41(m,3H),7.38-7.35(m,2H),7.25-7.22(m,2H),3.83(s,2H,CageC-H),2.37(s,3H,-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ137.9,133.9,133.2,130.6,130.2,128.3,59.1,29.7,21.5,1.1; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-3.8[2B,B(3)-Ph&B(6)-Ph],-11.4(2B),-13.0(4B); HRMS: calculated for C 15 H 22 B 10 - (MH) - 311.2579, found 311.2583.

[0106] Implementation Case 9

[0107]

[0108] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction bottle, compound 1a (22 mg, 0.1 mmol), compound 2i (61 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air conditions for 24 h. After the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3i was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 25.3 mg of product 3i with a yield of 78%. 1 H NMR (500MHz, CDCl3, ppm): δ7.62-7.61 (d, 2H, J = 5Hz), 7.44-7.41 (m, 1H), 7.37 (t, 1H, J = 5Hz), 7.3 1-7.28(m,1H),7.17-7.16(d,2H,J=5Hz),6.96-6.94(m,1H),3.84(s,3H,-CH3),3.83,(s,2H,Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ159.3,133.2,129.8,129.6,128.3,125.3,119.2,114.9,59.1,55.3,29.7; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-3.9[2B,B(3)-Ph&B(6)-Ph],-11.3(2B),-12.9(4B); HRMS: calculated for C 15 H 22 B 10 O - (MH) - 327.2528, found 327.2527.

[0109] Implementation Case 10

[0110]

[0111] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 2k (56 mg, 0.4 mmol), 1 ml of THF, dichloro(pentamethylcyclopentadienyl)iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol), and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 31.1 mg of product 3k in a 98% yield. 1 H NMR (500MHz, CDCl3, ppm): δ7.62-7.58(m,4H),7.44-7.41(m,1H),7.38-7.36(m,2H),7.08-7.04(m,2H),3.82(s,2H,Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ165.0,163.3,135.1,133.2,129.9,128.4,115.6,115.4,59.1; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.1(2B),-3.9[2B,B(3)-Ph&B(6)-Ph],-11.3(2B),-13.0(4B); HRMS: calculated for C 14 H 19 B 10 F - (MH) - 315.2328, found 315.2330.

[0112] Implementation Case 11

[0113]

[0114] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 21 (62 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence, and the mixture was reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the mixture was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 32.3 mg of product 31 in a yield of 98%. 1 H NMR (500MHz, CDCl3, ppm): δ7.62-7.61 (d, 2H, J = 5Hz), 7.55-7.54 (d, 2H, J = 5Hz), 7.43 (t, 1H, J = 5Hz), 7.38-7.34 (m, 4H), 3.82 (s, 2H, Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ136.4,134.5,133.2,129.9,128.6,128.4,59.0,29.7; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-1.9(2B),-3.6[2B,B(3)-Ph&B(6)-Ph],-11.0(2B),-12.7(4B); HRMS: calculated for C 14 H 19 B 10 Cl - (MH) - 331.2076,found331.2063.

[0115] Implementation Case 12

[0116]

[0117] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 2m (80 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 34.6 mg of product 3m in a yield of 92%. 1 H NMR (500MHz, CDCl3, ppm): δ7.62-7.61 (d, 2H, J = 5Hz), 7.52-7.47 (m, 4H), 7.45-7.42 (m, 1H), 7.39-7.36 (m, 2H), 3.82 (s, 2H, CageC-H); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ134.7,133.2,131.5,129.9,128.4,124.8,59.0,29.7; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.0(2B),-3.8[2B,B(3)-Ph&B(6)-Ph],-11.2(2B),-12.9(4B); HRMS: calculated for C 14 H 19 B 10 Br - (MH) - 375.1580, found 375.1577.

[0118] Implementation Case 13

[0119]

[0120] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction bottle, compound 1a (22 mg, 0.1 mmol), compound 2n (75.6 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence, and the reaction was carried out at room temperature under air conditions for 24 h. After the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3n was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 26.6 mg of the product 3n in a yield of 72%. 1 H NMR (500MHz, CDCl3, ppm): δ7.75-7.74 (d, 2H, J = 5Hz), 7.63-7.62 (d, 4H, J = 5Hz), 7.45-7.42 (m, 1H), 7.39-7.37 (m, 2H), 3.86 (s, 2H, Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ133.5,133.2,132.0,131.8,130.0,128.4,125.0,124.8,58.9,29.7; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.0(2B),-3.6[2B,B(3)-Ph&B(6)-Ph],-11.3(2B),-12.9(4B); HRMS: calculated for C 15 H 19 B 10 F3 - (MH) - 365.2296, found 365.2300.

[0121] Implementation Case 14

[0122]

[0123] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 2o (56 mg, 0.4 mmol), 1 ml of THF, dichloro(pentamethylcyclopentadienyl)iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol), and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3o was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 22.5 mg of the product 3o in a yield of 71%. 1 H NMR (500MHz, CDCl3, ppm): δ7.63-7.61 (d, 2H, J = 10Hz), 7.44-7.42 (m, 1H), 7.39-7.30 (m, 5H), 7.13-7.09 (m, 1H), 3.84 (s, 2H, CageC-H); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): 133.2, 129.9, 128.7, 128.4, 120.0, 116.9,, 59.0, 32.0, 29.7, 22.7, 14.2; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.1(2B),-3.7[1B,B(3)-Ph],-4.6[1B,B(6)-Ph],-11.2(2B),-13.0(4B); HRMS: calculated for C 14 H 19 B10 F - (MH) - 315.2328,found 315.2328.

[0124] Implementation Case 15

[0125]

[0126] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 1a (22 mg, 0.1 mmol), compound 2p (56 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 3p was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 29.9 mg of the product 3p in a yield of 94%. 1 H NMR (500MHz, CDCl3, ppm): δ7.85(t,1H,J=5Hz),7.64-7.63(d,2H,J=5Hz),7.45-7.37(m,4H),7.22(t,3H,J=10Hz),7.03-6.99(m,1H,),4.18(s,2H,Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ165.8,164.2,138.0,133.1,131.8,129.8,128.3,124.8,115.3,115.1,58.3,29.7; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.6(2B),-4.4[1B,B(3)-Ph],-6.1[1B,B(6)-Ph],-10.6(2B),-12.2(4B).

[0127] Implementation Case 16

[0128]

[0129] According to the method of Example 1, the reaction conditions are as follows: to a 10ml reaction flask, compound 4a (24mg, 0.1mmol), compound 2b (54mg, 0.4mmol), THF 1ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8mg, 0.01mmol), silver hexafluoroantimonate (25mg, 0.1mmol), silver tetrafluoroborate (80mg, 0.4mmol), cesium fluoride (45mg, 0.3mmol) and water (7.2mg, 0.4mmol) were added in sequence and reacted at room temperature under air for 24h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5a was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as eluent to obtain 17.2mg of product 5a in a yield of 53%. 1 H NMR (500MHz, CDCl3, ppm): δ7.51-7.50 (d, 4H, J = 5Hz), 7.19-7.18 (d, 4H, J = 5Hz), 3.81 (s, 2H, Cage CH), 2.36 (s, 6H, -CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ139.9,133.2,129.1,59.2,21.4; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-3.6[2B,B(3,6)-Ph],-11.5(2B),-13.0(4B).

[0130] Implementation Case 17

[0131]

[0132] According to the method of Example 1, the reaction conditions are as follows: to a 10ml reaction flask, compound 4b (25mg, 0.1mmol), compound 2c (75mg, 0.4mmol), THF 1ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8mg, 0.01mmol), silver hexafluoroantimonate (25mg, 0.1mmol), silver tetrafluoroborate (80mg, 0.4mmol), cesium fluoride (45mg, 0.3mmol) and water (7.2mg, 0.4mmol) were added in sequence and reacted at room temperature under air for 24h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5b was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as eluent to obtain 20.9mg of the product 5b in a 60% yield. 1H NMR (500MHz, CDCl3, ppm): δ7.54-7.53(d,4H,J=5Hz),7.21-7.20(d,4H),3.82(s,2H,Cage CH),2.68-2.64(q,4H,J=6Hz,-CH2-),1.24(t,6H,-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ146.2,133.3,127.9,127.7,59.2,28.8,15.5; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.4(2B),-3.4[2B,B(3)-Ph&B(6)-Ph],-11.5(2B),-13.0(4B).

[0133] Implementation Case 18

[0134]

[0135] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 4c (25 mg, 0.1 mmol), compound 2e (61 mg, 0.4 mmol), 1 ml of THF, dichloro(pentamethylcyclopentadienyl)iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol), and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5c was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 6.3 mg of the product 5c in an 18% yield. 1 H NMR (500MHz, CDCl3, ppm): δ7.54-7.53 (d, 4H, J = 5Hz), 6.90-6.89 (d, 4H, J = 5Hz), 3.82 (s, 6H, CH3), 3.78 (s, 2H, Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ161.0,134.6,113.9,129.9,59.3,55.3; 11 B{ 1H}NMR (160MHz, CDCl3, ppm): δ-2.4(4B),-11.6(2B),-13.1(4B); HRMS: calculated for C 14 H 19 B 10 Br - (MH) - 375.1580, found 375.1577.

[0136] Implementation Case 19

[0137]

[0138] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 4d (30 mg, 0.1 mmol), compound 2q (76 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air conditions for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5d was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 34.7 mg of product 5d in an 83% yield. 1 H NMR (500MHz, CDCl3, ppm): δ8.02-8.01 (d, 4H, J = 5Hz), 7.70-7.69 (d, 4H, J = 5Hz), 4.40-4.36 (q, 4H, J = 5Hz, -CH2-), 3.91 (s, 2H, Cage CH),1.40(t,6H,J=5Hz,-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ166.3,133.2,131.8,129.2,115.1,61.3,58.8,14.3; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-1.8(2B),-4.3[2B,B(3,6)-Ph],-10.8(2B),-12.7(4B).

[0139] Implementation Case 20

[0140]

[0141] According to the method of Example 1, the reaction conditions are as follows: To a 10 ml reaction flask, compound 4e (30 mg, 0.1 mmol), compound 2m (80 mg, 0.4 mmol), 1 ml of THF, dichloro(pentamethylcyclopentadienyl)iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol), and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5e was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 33.2 mg of the product 5e in a 73% yield. 1 H NMR (500MHz, CDCl3, ppm): δ7.52-7.50 (dt, 4H, J = 5, 10Hz), 7.48-7.46 (dt, 4H, J = 5, 10Hz), 3.79 (s, 2H, Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ134.7,131.6,124.9,58.8; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-1.9(2B),-4.1[2B,B(3,6)-Ph],-11.1(2B),-12.9(4B).

[0142] Implementation Case 21

[0143]

[0144] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction bottle, compound 4f (25 mg, 0.1 mmol), compound 21 (62 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air conditions for 24 h. After the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5f was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as eluent to obtain 28.9 mg of the product 5f with a yield of 76%. 1H NMR (500MHz, CDCl3, ppm): δ7.55-7.53 (dt, 4H, J = 5, 10Hz), 7.36-7.34 (dt, 2H, J = 5, 10Hz), 3.80 (s, 2H, Cage CH); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ136.5,134.5,128.6,58.9; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.0(2B),-4.3[2B,B(3,6)-Ph],-11.2(2B),-13.0(4B).

[0145] Implementation Case 22

[0146]

[0147] According to the method of Example 1, the reaction conditions are as follows: to a 10ml reaction flask, compound 4g (25mg, 0.1mmol), compound 2i (61mg, 0.4mmol), THF 1ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8mg, 0.01mmol), silver hexafluoroantimonate (25mg, 0.1mmol), silver tetrafluoroborate (80mg, 0.4mmol), cesium fluoride (45mg, 0.3mmol) and water (7.2mg, 0.4mmol) were added in sequence and reacted at room temperature under air for 24h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product was separated by column chromatography using petroleum ether:ethyl acetate (20:1) as the eluent to obtain 5g (30.8mg) of the product with a yield of 68%. 1 H NMR (500MHz, CDCl3, ppm): δ7.41-7.36(m,3H),7.27-7.26(m,3H),7.07-7.05(m,2H),3.94(m,8H,Cage CH&-CH3); 13 C{ 1 H}NMR (125MHz, CDCl3, ppm): δ159.3,129.6,125.3,119.2,114.9,59.1,55.3,29.7; 11 B{ 1 H}NMR (160MHz, CDCl3, ppm): δ-2.3(2B),-4.0[2B,B(3)-Ph&B(6)-Ph],-11.4(2B),-12.9(4B).

[0148] Implementation Case 23

[0149]

[0150] According to the method of Example 1, the reaction conditions are as follows: to a 10 ml reaction flask, compound 4h (24 mg, 0.1 mmol), compound 2a (56 mg, 0.4 mmol), THF 1 ml, dichloro (pentamethylcyclopentadienyl) iridium dimer (8 mg, 0.01 mmol), silver hexafluoroantimonate (25 mg, 0.1 mmol), silver tetrafluoroborate (80 mg, 0.4 mmol), cesium fluoride (45 mg, 0.3 mmol) and water (7.2 mg, 0.4 mmol) were added in sequence and reacted at room temperature under air for 24 h. After completion of the reaction, ethyl acetate was added to quench the reaction, and the inorganic salts were removed by filtration through a short silica gel column. After concentration under reduced pressure, the product 5h was separated by column chromatography using petroleum ether: ethyl acetate (20:1) as the eluent to obtain 23.5 mg of the product 5h in a yield of 71%. 1 H NMR (500MHz, CDCl3, ppm): δ7.38-7.30(m,6H),7.13-7.10(m,2H),3.83(s,2H,Cage CH); 13 C{ 1 H}NMR (150MHz, CDCl3, ppm): δ163.5,1618,130.2,128.7,120.0,117.0,59.0,29.7; 11 B{ 1 H}NMR (192MHz, CDCl3, ppm): δ-2.0(2B),-4.5[2B,B(3,6)-Ph],-11.0(2B),-12.9(4B).

[0151] The above embodiments illustrate the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and improvements may be made to the present invention without departing from the scope of the principles of the present invention, and all such changes and improvements fall within the scope of protection of the present invention.

Claims

1. A method for selective arylation of o-carborane B(6)-H, characterized in that: The method comprises the following steps: using o-carborane 1 and arylboronic acid 2 as raw materials, reacting in the presence of a catalyst (pentamethylcyclopentadienyl)iridium dimer, silver hexafluoroantimonate, silver tetrafluoroborate, cesium fluoride, water, and tetrahydrofuran to obtain B(3,6)-diaryl-o-carborane 3; the reaction equation is expressed as follows: Wherein R is selected from one or more of hydrogen, methyl, ethyl, phenyl, tert-butyl, naphthyl, methoxy, ester, trifluoromethyl, and halogen.

2. The method for selective arylation of o-carborane B(6)-H according to claim 1, characterized in that: The reaction was carried out in air without inert gas protection.

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