Norbornane skeleton monophosphine ligand and its borane adduct, palladium complex and preparation method and application thereof

Abstract

This invention discloses a norbornene skeleton monophosphine ligand, its borane adduct, palladium complex, its preparation method, and its application. The norbornene skeleton monophosphine ligand is prepared through the following steps: using a palladium metal complex as a catalyst, and triethylamine and formic acid as negative hydrogen sources, in a solvent, bromonorbornene and its analogues undergo a hydroarylation reaction with ArX, where X in ArX is I, Br, or OTf, to obtain an aryl-substituted bromonorbornene skeleton. The aryl-substituted bromonorbornene skeleton undergoes a lithium bromide exchange with tert-butyllithium, followed by R... 1 R 2 PCl undergoes a substitution reaction to prepare the norcamphor skeleton monophosphine ligand, and the norcamphor skeleton monophosphine ligand-palladium complex exhibits good catalytic activity in the Suzuki coupling reaction.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to norcamphene skeleton monophosphine ligands and their borane adducts, palladium complexes, their preparation methods and applications. Background Technology

[0002] Transition metal-catalyzed organic synthesis reactions have crucial applications and have long been a focus of attention. Ligands can modulate the electronic properties and spatial structure of the metal center, thereby affecting the catalytic performance of metal complexes. Therefore, ligands occupy a central position in transition metal catalysis. An important direction in transition metal catalysis research is the development of novel ligands. Among the many ligands, phosphine ligands are undoubtedly the most widely used. In ligand design, the skeleton significantly influences the stability, activity, and selectivity of the ligand. For example, the chiral spirocyclic phosphine ligands developed by Zhou Qilin's research group greatly promoted the development of reactions such as asymmetric hydrogenation (Acc. Chem. Res. 2008, 41, 581); the biaryl phosphine ligands designed by Buchwald's research group greatly promoted the development of CN bond coupling (Chem. Rev., 2016, 116, 12564); and the indenephosphine ligands and palladium-coated catalysts developed by Yu Guang'ao's research group showed high activity in the Suzuki-Miyaura coupling reaction, with catalyst dosage as low as 0.01 mol% and a conversion number (TON) of up to 9800 (Org. Biomol. Chem., 2017, 15, 3924).

[0003] The academic and industrial communities have long been interested in designing and synthesizing novel phosphine ligands and catalysts to develop more promising new catalytic reactions. Norbornenes are molecules with unique rigid structures, and the preparation of phosphine ligands using norbornenes as a backbone holds promise for further improving catalytic performance and expanding the application range of existing phosphine ligands. However, in current technology, the synthesis of phosphine ligands with a norbornene backbone and their application in catalytic reactions are still in the exploratory stage, and research on related preparation methods is relatively limited. Therefore, developing a novel single-phosphine ligand with a norbornene backbone and its preparation method has significant scientific value and application prospects. Summary of the Invention

[0004] The purpose of this invention is to address the technical deficiencies in the prior art by providing a norcamphor skeleton monophosphine ligand and its adduct with borane.

[0005] Another object of the present invention is to provide a method for preparing the said norcamphor skeleton monophosphine ligand and its adduct with borane.

[0006] Another object of the present invention is to provide a norcamphor skeleton monophosphine ligand-palladium complex.

[0007] Another object of the present invention is to provide the norcamphor skeleton monophosphine ligand, the adduct of the norcamphor skeleton monophosphine ligand and borane, and applications based on the norcamphor skeleton monophosphine ligand-palladium complex.

[0008] The technical solution adopted to achieve the purpose of this invention is:

[0009] A norunane skeleton monophosphine ligand having the following structural formula or its enantiomer or racemate:

[0010]

[0011] in:

[0012] Ar is an aryl group;

[0013] R 1 R 2 The substituent is aryl or aliphatic, wherein the aliphatic substituent includes alkyl, alkenyl, or ynyl, R 1 R 2 Same or different;

[0014] R 3 ~R 6 It is one or more of H, C1-C8 alkyl, C2-C8 acyloxy, hydroxyl, halogen, amino, (C1-C8 acyl)amino, di(C1-C8 alkyl)amino, C1-C8 acyl, C2-C8 ester, haloalkane, silyl, and heteroatom substituent; R 1 ~R 6 Same or different;

[0015] When there are substituents in the aryl group, the substituents are one or more of the following: C1-C8 alkyl, C2-C8 acyloxy, hydroxyl, halogen, amino, (C1-C8 acyl)amino, di(C1-C8 alkyl)amino, C1-C8 acyl, C2-C8 ester, haloalkane, silyl, heteroatom substituents; the number of substituents is 0-5.

[0016] In the above technical solutions, the C1-C8 alkyl group is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, sec-octyl, or tert-octyl.

[0017] The C1-C8 acyl groups are formyl, acetyl, propionyl, n-butyryl, isobutyryl, n-valeryl, isovaleryl, sec-valeryl, neovaleryl, n-hexanoyl, isohexanoyl, neohexanoyl, sec-hexanoyl, n-heptanoyl, isoheptanoyl, neoheptanoyl, sec-heptanoyl, n-octanoyl, isooctanoyl, neoctanoyl, sec-octanoyl, 1-cyclopropylformyl, 1-cyclobutylformyl, 1-cyclopentylformyl, 1-cyclohexylformyl, 1-cycloheptylformyl;

[0018] The C2-C8 acyloxy groups are acetyloxy, propionyloxy, n-butyryloxy, isobutyryloxy, n-valeryloxy, isovaleryloxy, sec-valeryloxy, neovaleryloxy, n-hexanoyloxy, isohexanoyloxy, neohexanoyloxy, sec-hexanoyloxy, n-heptanoyloxy, isoheptanoyloxy, neoheptanoyloxy, sec-heptanoyloxy, n-octanoyloxy, isooctanoyloxy, neoctanoyloxy, sec-octanoyloxy, 1-cyclopropylformyloxy, 1-cyclobutylformyloxy, 1-cyclopentylformyloxy, 1-cyclohexylformyloxy, 1-cycloheptylformyloxy;

[0019] The C2-C8 ester groups are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, secondary pentoxycarbonyl, tertiary pentoxycarbonyl, cyclopentoxycarbonyl, n-hexyloxycarbonyl, isohexyloxycarbonyl, neohexyloxycarbonyl, secondary hexyloxycarbonyl, tertiary hexyloxycarbonyl, cyclohexyloxycarbonyl, n-heptyloxycarbonyl, isoheptyloxycarbonyl, neoheptyloxycarbonyl, secondary hexyloxycarbonyl, tertiary hexyloxycarbonyl, and cycloheptyloxycarbonyl.

[0020] Preferably, the haloalkane is a fluorine-, chlorine-, bromine-, or iodine-containing haloalkane.

[0021] In the above technical solution, the norcamphor skeleton monophosphine ligand structure is a structure of 1-a, 1-b, 1-c, 1-d, 1-e, 1-f or 1-g, or an enantiomer or racemate of the following structures:

[0022]

[0023] Another aspect of the present invention includes a method for preparing the norcamphor skeleton monophosphine ligand, comprising the following steps:

[0024] Step 1: Using a palladium metal complex as a catalyst and triethylamine and formic acid as negative hydrogen sources, in a solvent, bromonorbornene and its analogues, as shown in formula 4, undergo a hydroarylation reaction with ArX, where X in ArX is I, Br, or OTf, to prepare an aryl-substituted bromonorbornene skeleton, as shown in formula 2. The reaction formula is as follows:

[0025]

[0026] Step 2: After the aryl-substituted bromonorbornene skeleton of structure 2 undergoes a bromide-lithium exchange with tert-butyllithium, it is then reacted with R... 1 R 2 PCl undergoes a substitution reaction to prepare the norcamphorane skeleton monophosphine ligand as shown in Formula 1, as follows:

[0027]

[0028] Preferably, the solvent in step 1 is one or more of dimethyl sulfoxide, benzene, toluene, tetrahydrofuran, ethyl acetate, and acetonitrile, the reaction temperature is 0-120℃, and the reaction time is 1-24 hours.

[0029] Another aspect of the present invention includes the adduct of the norcamphorane skeleton monophosphine ligand and borane, having the following structural formula 3, or an enantiomer or racemate of the following structural formula 3:

[0030]

[0031] In another aspect of the present invention, the preparation method of the adduct comprises the following steps: reacting a norbornene skeleton monophosphine ligand of structural formula 1 with a tetrahydrofuran solution of borane to generate the corresponding adduct of structural formula 3, wherein the reaction formula is as follows:

[0032]

[0033] Alternatively, the aryl-substituted bromonorbornene skeleton of structure 2 can undergo bromolithium exchange with tert-butyllithium, followed by R. 1 R 2 PCl undergoes a substitution reaction, followed by the addition of a tetrahydrofuran solution of borane to prepare the adduct as shown in Figure 3, with the following reaction formula:

[0034]

[0035] In the above technical solution, the aryl-substituted norbornene skeleton is prepared by the following steps: using a palladium metal complex as a catalyst, and triethylamine and formic acid as negative hydrogen sources, in a solvent, norbornene and its analogues with structural formula as shown in 4 undergo a hydroarylation reaction with ArX, where X in ArX is I, Br, or OTf, to prepare the aryl-substituted norbornene skeleton with structural formula as shown in 2; the reaction formula is as follows:

[0036]

[0037] Another aspect of the present invention includes palladium complexes based on the said norbornene skeleton monophosphine ligands, having the following 5 structural formulas, or enantiomers or racemates of the following 5 structural formulas:

[0038]

[0039] X and Y are halogens, acid radicals, 1,3-dicarbonyl ligands, allyl or aryl groups, and X and Y may be the same or different.

[0040] Another aspect of the present invention includes a method for preparing the palladium complex:

[0041] The palladium complex is obtained by reacting the norcamphor skeleton monophosphine ligand, or the adduct of the norcamphor skeleton monophosphine ligand and borane with palladium salt and XY in a solvent, followed by separation and purification.

[0042] In the above technical solution, the palladium salt is one or more of (COD)Pd(CH2TMS)2, Pd2(dba)3.CHCl3, Pd2(dba)4, Pd(OAc)2, Pd(TFA)2 or [(allyl)PdCl]2.

[0043] Another aspect of the invention includes the use of the palladium complex as a catalyst in the catalytic Suzuki coupling reaction.

[0044] Another aspect of the present invention includes the application of the norcamphor skeleton monophosphine ligand or the adduct of the norcamphor skeleton monophosphine ligand and borane, together with palladium salt, as a catalytic system in the catalytic Suzuki coupling reaction. Attached Figure Description

[0045] Figure 1 Single crystal structure of 3-d borane adduct of monophosphine ligand in the norcanane framework

[0046] Figure 2 Single-crystal structure of the norcanane framework monophosphine ligand 1-e Detailed Implementation

[0047] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0048] The following examples use abbreviations, whose meanings are as follows:

[0049] Me is a methyl group. t Bu is tert-butyl, Ph is phenyl, DMSO is dimethyl sulfoxide, THF is tetrahydrofuran, PE is petroleum ether, EA is ethyl acetate, DCM is dichloromethane, and DABCO is triethylenediamine.

[0050] eq stands for equivalent, rt represents room temperature, TLC stands for thin-layer chromatography, NMR stands for nuclear magnetic resonance, and HRMS stands for high-resolution mass spectrometry.

[0051] All solvents used were purified and dried according to standard procedures before use; all reagents used were commercially available or synthesized according to existing literature methods, and were purified before use.

[0052] The 7-bromo-2-phenylbicyclo[2,2,1]hept-2-ene (4-a) used in the following examples was prepared by the following steps:

[0053]

[0054] Add 20 g (212 mmol) of bicyclo[2,2,1]hept-2-ene to a 500 mL single-necked flask, add 200 mL of dichloromethane, stir to dissolve, and rapidly add 81.5 g (255 mmol) of pyridine tribromide at -78 °C. Stir for 1 hour, then remove to room temperature and continue the reaction for 8 hours. After the reaction is complete, wash the system with saturated sodium bicarbonate aqueous solution (150 mL * 3) and sodium thiosulfate aqueous solution (150 mL * 3), dry with anhydrous magnesium sulfate, filter, evaporate the solvent, and purify the product by vacuum distillation. Collect the fraction at 1.5 Pa and 50 °C to obtain 29.6 g of colorless oily product 2,7-dibromobicyclo[2,2,1]heptane, 55% yield.

[0055] The NMR spectral data are consistent with those reported in the literature [Gueltekin, DD, Taskesenligil, Y., Dastan, A. & Balci, M. Tetrahedron 2008, 64, 4377-4383].

[0056] Potassium tert-butoxide (35.4 g, 315 mmol) was added to a 500 mL two-necked flask to replace the atmosphere with argon. 200 mL of ultra-dry tetrahydrofuran was added, followed by 20 g of 2,7-dibromobicyclo[2,2,1]heptane (78.8 mmol) at 0 °C. The mixture was stirred at room temperature for 48 hours. After the reaction was complete, 200 mL of diethyl ether was added to the system, and the mixture was washed with saturated brine (200 mL x 3). The aqueous phase was extracted with diethyl ether (200 mL x 3). The organic phases were combined, and the solvent was carefully removed by rotary evaporation to give a colorless oily product 4-a, 13.0 g, 96% yield.

[0057] The NMR spectral data are consistent with those reported in the literature [Gueltekin, DD, Taskesenligil, Y., Dastan, A. & Balci, M. Tetrahedron 2008, 64, 4377-4383].

[0058] The 9-bromo-1,4-dihydro-1,4-methylenenaphthalene (4 g) used in the following examples was prepared by the following steps:

[0059]

[0060] Add the reactants 2,9-dibromo-1,2,3,4-tetrahydro-1,4-methylenenaphthalene (4.302 g, 14.2 mmol) and potassium tert-butoxide (5.652 g, 56.8 mmol) to a 100 mL double-necked flask, replace with argon gas, add 50 mL of dry tetrahydrofuran, stir at room temperature, and after 24 hours, the reaction is confirmed to be complete by TLC. Remove the solvent by rotary evaporation, add 100 mL of ethyl acetate, wash with water (100 mL * 3), filter the organic phase after drying with anhydrous magnesium sulfate, and separate by silica gel column chromatography (eluent: PE / EA 100:1, v / v) to obtain 2.998 g of product, 96% yield, white solid, melting point 58℃-60℃.

[0061] 1 H NMR (600MHz, Chloroform-d) δ7.23(dd,J=5.3,3.1Hz,2H),7.00(dd,J=5.3,3.1Hz,2H),6.71-6.70(m,2H),4.37(s,1H),4.06(q,J=1.7Hz,2H).

[0062] 13 C NMR(151MHz,Chloroform-d)δ147.2,139.7,125.8,122.2,74.4,57.4.

[0063] The N,N,N',N'-tetramethyl(o-methylphenyl)phosphine diamine (L1) used in the following examples was prepared by the following steps:

[0064]

[0065] A 250 mL double-necked flask was purged with argon atmosphere. 200 mL of ultra-dry tetrahydrofuran and 3.42 g (20 mmol) of o-bromotoluene were added. A 2.5 M in pentane solution (10 mL, 1.2 eq) was added dropwise at -78 °C, and the mixture was stirred overnight. Then, N,N,N',N'-tetramethyldiaminophosphine chloride (3.25 g, 21 mmol) was added at -78 °C, and the mixture was slowly heated to room temperature and reacted for 6 hours. After the reaction was complete, 200 mL of dichloromethane was added to the system, and the mixture was washed with saturated brine (200 mL x 3). The aqueous phase was extracted with dichloromethane (200 mL x 3). The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation to obtain a colorless oily product L1, 3.11 g, 74% yield.

[0066] The NMR spectral data are consistent with those reported in the literature [Xu, Y.; Alcock, NW; Clarkson, GJ; Docherty, G.; Woodward, G.; Wills, M. Org. Lett. 2004, 6, 4105-4107.].

[0067] Example 1

[0068] 2-Phenylanbicyclo[2,2,1]heptyl-7-diphenylphosphine (1-a) was prepared by the following steps:

[0069] Step 1: Using palladium acetate and L1 as catalysts, and triethylamine and formic acid as negative hydrogen sources, bromonorbornene and iodobenzene undergo a hydroarylation reaction in a solvent to prepare 7-bromo-2-phenylbicyclo[2,2,1]heptane (2-a):

[0070]

[0071] Palladium acetate (0.112 g, 0.5 mmol) was added to a 250 mL double-necked flask. A reflux filtration device was added, and the atmosphere was replaced with argon gas by purging with cooling water. DMSO (250 mL) and N,N,N',N'-tetramethyl(o-methylphenyl)phosphine diamine L1 (0.22 g, 1.05 mmol) were added. The mixture was heated and stirred at 60 °C for 10 minutes. After cooling to room temperature, triethylamine (17.7 g, 175 mmol), formic acid (6.91 g, 150 mmol), 7-bromo-2-phenylbicyclo[2,2,1]hept-2-ene (8.65 g, 50 mmol), and iodobenzene (20.4 g, 100 mmol) were added sequentially. The mixture was stirred at 120 °C. After the reaction was completed as detected by TLC, the mixture was cooled to room temperature, poured into water, extracted with dichloromethane, dried, filtered, and the solvent was removed by rotary evaporation. The product was then purified by silica gel column chromatography (eluent: PE / EA). (100:1, v / v) to obtain 10.3 g of colorless oily product, yield 82%.

[0072] 1 H NMR(600MHz,Chloroform-d)δ7.36(d,J=7.8Hz,2H),7.32-7.29(m,2H),7.19-7.17(m,1H),4.00(s,1H),3. 03-3.00(m,1H),2.95(s,1H),2.53-2.49(m,2H),2.08-2.05(m,1H),1.78-1.76(m,2H),1.54-1.48(m,2H).

[0073] 13C NMR (151MHz, Chloroform-d) δ145.3,127.9,127.1,125.4,56.4,56.3,46.4,46.0,43.8,36.8,30.1,26.3.

[0074] Step 2: 7-Bromo-2-phenylbicyclo[2,2,1]heptane (2-a) undergoes a bromide-lithium exchange reaction with tert-butyllithium, followed by a substitution reaction with diphenylphosphine chloride to prepare 2-phenylbicyclo[2,2,1]heptyl-7-diphenylphosphine (1-a). This is then prepared through the following steps.

[0075]

[0076] 2-a (1.004 g, 4 mmol) was added to a dry 100 mL two-necked flask to displace argon gas. 20 mL of dry tetrahydrofuran was added, and the mixture was stirred at -78 °C. Tert-butyllithium (1.3 M in pentane, 7.7 mL, 10 mmol) was slowly added dropwise, and stirring continued at -78 °C for 3 hours. Diphenylphosphine chloride (2.652 g, 12 mmol) was added dropwise, and the mixture was slowly brought to room temperature and stirred for 12 hours. The solution was carefully quenched with water at 0 °C. After removing the solvent by rotary evaporation, the product was separated by silica gel column chromatography (eluent: PE / EA20:1, v / v) to give 814.6 mg of the product (55% yield), a colorless oil.

[0077] 1 H NMR(600MHz,Chloroform-d)δ7.25-7.22(m,2H),7.20-7.11(m,10H),7.09-7.07(m,1H),7.02-7.00(t,J=7.2Hz,2H),2.82(t,J=7.9Hz, 1H),2.63-2.59(m,1H),2.55(s,1H),2.33(s,1H),2.27(d,J=6.3Hz,1H),1.87(t,J=10.7Hz,1H),1.70-1.65(m,2H),1.48-1.40(m,2H).

[0078] 13C NMR(151MHz,Chloroform-d)δ145.3(d,J=1.4Hz),133.8(d,J=19.5Hz),132.4 (d,J=18.8Hz),128.5,128.30,128.26,128.20,128.15,128.06,127.9,127.5( d,J=3.6Hz),125.4,50.8(d,J=15.4Hz),46.4(d,J=1.4Hz),45.5(d,J=7.9Hz) ,41.3(d,J=13.8Hz), 36.1(d,J=9.2Hz), 33.1(d,J=8.0Hz), 29.8(d,J=5.8Hz).

[0079] 31 P NMR(243MHz,Chloroform-d)δ-21.53.

[0080] HRMS(ESI)calcd for [M+H] + :357.1767,found:357.1767.

[0081] Example 2

[0082] Because the structure of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-b) is easily oxidized, borane is used to protect it during actual production and transportation. Specifically, the preparation method of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine borane adduct (3-b) is as follows:

[0083]

[0084] Add 2-a (1.004 g, 4 mmol) to a dry 100 mL two-necked flask, purging with argon gas. Add 20 mL of dry tetrahydrofuran, stir at -78 °C, and slowly add tert-butyllithium (1.3 M in pentane, 7.7 mL, 10 mmol) dropwise, continuing stirring at -78 °C for 3 hours. Add dicyclohexylphosphine chloride (2.796 g, 12 mmol) dropwise, slowly return to room temperature, and continue stirring for 12 hours. Slowly add borane tetrahydrofuran solution dropwise at 0 °C, and stir at room temperature for 4 hours. Carefully quench with water. After removing the solvent by rotary evaporation, separate by silica gel column chromatography (eluent: PE / EA 20:1, v / v). Recrystallize the obtained solid using the PE / EA system to give 730 mg of product, 48% yield, a white solid with a melting point of 187 °C–189 °C.

[0085] 1H NMR(600MHz,Chloroform-d)δ7.39(d,J=7.6Hz,2H),7.32-7.29(m,2H),7.17-7.15(m,1H),2.94(t,J=8.3Hz,1H),2.81 (s,1H),2.75-2.71(m,1H),2.64(s,1H),1.79-1.44(m,19H),1.26-1.11(m,4H),1.05-0.88(m,4H),0.55-0.07(m,4H).

[0086] 13 C NMR(151MHz,Chloroform-d)δ143.2,128.13,128.09,126.0,47.7(d,J=1.9Hz),46.1,45.5( d,J=29.8Hz),41.6(d,J=2.7Hz),35.9(d,J=33.6Hz),34.4,34.2(d,J=10.6Hz),33.4(d,J=30 .3Hz),29.0(d,J=11.0Hz),28.0(d,J=6.4Hz),27.20,27.17(d,J=5.5Hz),27.08(d,J=15.1Hz ).26.9(d,J=1.4Hz),26.88,26.7(d,J=10.5Hz),26.6,26.2(d,J=1.5Hz),26.0(d,J=1.4Hz).

[0087] 31 P NMR (243MHz, Chloroform-d) δ19.79 (d, J=69.3Hz).

[0088] 11 B NMR (193MHz, Chloroform-d) δ-43.40 (d, J = 52.6Hz).

[0089] HRMS(ESI)calcd for [M+Na] + :405.2853,found:405.2845.

[0090] The method for preparing 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-b) using the 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine borane adduct (3-b) is as follows:

[0091]

[0092] 3-B (382 mg, 1 mmol) and triethylenediamine (DABCO, 336.6 mg, 3 mmol) were added to a 50 mL double-necked flask to replace the argon gas. 10 mL of dry tetrahydrofuran was added, and the mixture was heated at 65 °C for 12 hours. After the reaction was confirmed to be complete by TLC, the solvent was evaporated and the mixture was separated by silica gel column chromatography (eluting agent: PE / EA 100:1, v / v). 365 mg of the product was obtained, with a yield of 99%, as a colorless oil.

[0093] 1 H NMR(600MHz,Chloroform-d)δ7.38(d,J=7.7Hz,2H),7.27-7.26(m,2H),7.13-7.10(m,1H),2.82(t,J=7.9Hz,1H),2.68-2.64(m,1H), 2.55(d,J=3.5Hz,1H),2.36(s,1H),1.77-1.60(m,10H),1.55-1.40(m,6H),1.26-1.15(m,6H),1.05-0.98(m,4H),0.77-0.72(m,2H).

[0094] 13 C NMR(151MHz,Chloroform-d)δ144.6,128.0(d,J=3.8Hz),127.9,125.4,48.7(d,J=3.4Hz),47.1(d,J=20.1H z),47.0,42.5(d,J=15.2Hz),35.5(d,J=14.0Hz),34.4(d,J=14.8Hz),33.9(d,J=9.7Hz),33.4(d,J=5.4Hz), 32.2(d,J=18.0Hz),31.4(d,J=15.8Hz),30.3(d,J=11.6Hz),29.5(d,J=5.7Hz),28.4(d,J=1.4Hz),28.1(d, J=13.3Hz), 27.9(d,J=4.4Hz), 27.6(d,J=8.6Hz), 27.3(d,J=10.6Hz), 26.7(d,J=1.1Hz), 26.6(d,J=1.2Hz).

[0095] 31 P NMR(243MHz,Chloroform-d)δ-10.16.

[0096] HRMS(ESI)calcd for [M+H] + :369.2706,found:369.2693.

[0097] Example 3

[0098] Similar to the preparation method of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphoronane adduct (3-b) in Example 2, 2-phenylbicyclo[2,2,1]heptyl-7-diisopropylphosphoronane adduct (3-c) was prepared, with the following structural formula:

[0099]

[0100] White solid, yield 36%, melting point 145℃-147℃.

[0101] 1 H NMR(600MHz,Chloroform-d)δ7.35(d,J=8.0Hz,2H),7.30-7.27(m,2H),7.15-7.13 (m,1H),2.93(t,J=8.3Hz,1H),2.87(s,1H),2.77-2.73(m,1H),2.69(s,1H),1.88- 1.80(m,1H),1.79-1.70(m,3H),1.67-1.61(m,2H),1.50-1.46(m,1H),1.30-1.23( m,1H),1.13-1.09(m,6H),1.00-0.97(m,3H),0.83-0.79(m,3H),0.52-0.07(m,3H).

[0102] 13 C NMR(151MHz,Chloroform-d)δ142.9,128.0,127.8,125.9,47.2,46.0,45.4(d,J=29.6Hz),41.6,34.7,34.2(d ,J=10.9Hz),29.1(d,J=10.8Hz),25.3(d,J=34.2Hz),23.4(d,J=30.9Hz),18.3,17.9,17.7,16.8(d,J=5.3Hz).

[0103] 31 P NMR (243MHz, Chloroform-d) δ27.16 (d, J=72.8Hz).

[0104] 11 B NMR(193MHz,Chloroform-d)δ-43.72(d,J=58.7Hz).

[0105] HRMS(ESI)calcd for [M+Na] +:325.2227,found:325.2216.

[0106] Example 4

[0107] Similar to the preparation method of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphoronide adduct (3-b) in Example 2, 2-phenylbicyclo[2,2,1]heptyl-7-di-tert-butylphosphoronide adduct (3-d) was prepared, and its structure is as follows:

[0108]

[0109] White solid, yield 5%, melting point 184℃-186℃.

[0110] 1 H NMR(600MHz,Chloroform-d)δ7.32(d,J=7.3Hz,2H),7.28-7.22(m,2H),7.13 -7.11(m,1H),3.15(s,1H),2.95(t,J=8.6Hz,1H),2.91-2.85(m,2H),1.87(d, J=14.2Hz,1H),1.82-1.73(m,3H),1.69-1.65(m,1H),1.50-1.45(m,1H),1.29 (s,4.5H),1.27(s,4.5H),1.04(s,4.5H),1.02(s,4.5H),0.42--0.04(m,3H).

[0111] 13 C NMR(151MHz,Chloroform-d)δ142.9,127.8,127.7,125.5,48.8,46.0,42.4(d,J=1.4Hz),41.4(d,J=20.9Hz),35.2(d ,J=10.9Hz),34.7,34.3(d,J=27.2Hz),33.2(d,J=26.7Hz),29.0(d,J=1.3Hz),28.6(d,J=1.7Hz),28.4(d,J=9.9Hz).

[0112] 31 P NMR (243MHz, Chloroform-d) δ43.45 (d, J=77.3Hz).

[0113] 11 B NMR(193MHz,Chloroform-d)δ-42.40(d,J=56.2Hz).

[0114] HRMS(ESI)calcd for [M+Na] + :353.2540,found:353.2527.

[0115] Table 1: Single crystal test parameters of 3-d

[0116]

[0117]

[0118] Example 5

[0119] Similar to the preparation method of 7-bromo-2-phenylbicyclo[2,2,1]heptane (2-a) in Example 1, the difference is that the amount of palladium acetate is 0.05 eq, the amount of L1 is 0.1 eq, and iodobenzene is replaced with 1-iodonaphthalene to prepare 1-(7-bromobicyclo[2,2,1]heptyl)naphthalene (2-e), the structural formula of which is:

[0120]

[0121] 2-e is a white solid with a yield of 56% and a melting point of 105℃-107℃.

[0122] 1 H NMR(600MHz,Chloroform-d)δ8.03(d,J=8.6Hz,1H),7.90(d,J=8.6Hz,1H),7. 75(dd,J=11.3,7.7Hz,2H),7.56-7.53(m,1H),7.52-7.46(m,2H),4.06(s,1H) ,3.56(t,J=8.3Hz,1H),2.93(s,1H),2.67-2.63(m,1H),2.57(s,1H),2.19(dd ,J=12.4,9.1Hz,1H),1.90-1.80(m,2H),1.75-1.71(m,1H),1.70-1.65(m,1H).

[0123] 13 C NMR (151MHz, Chloroform-d) δ139.4,134.0,132.2,129.1,126.7,125.7,125.2,125.0,124.8,124.3,56.5,47.0,43.8,43.7,36.2,30.6,26.1.

[0124] Using 1-(7-bromobicyclo[2,2,1]heptyl)naphthalene (2-e) as a starting material, and employing a similar preparation method to that used for the 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphoronane adduct (3-b) in Example 2, the 2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphoronane adduct (3-e) was prepared, with the following structural formula:

[0125]

[0126] White solid, yield 47%, melting point 232℃-234℃.

[0127] 1 H NMR(600MHz,Chloroform-d)δ7.94(d,J=8.4Hz,1H),7.86(d,J=8.0Hz,1H),7.80(d,J=7.4Hz,1H),7.71( d,J=8.0Hz,1H),7.54-7.51(m,1H),7.49-7.45(m,2H),3.44(t,J=8.3Hz,1H),3.04-3.00(m,1H),2.81(s ,1H),2.74(s,1H),1.99-1.96(m,1H),1.87-1.74(m,4H),1.71-1.69(m,1H),1.65-1.45(m,10H),1.34-1 .07(m,8H),0.91-0.70(m,4H),0.27(q,J=12.8Hz,1H),0.05(q,J=12.8Hz,1H),-0.30(q,J=12.8Hz,1H).

[0128] 13 C NMR(151MHz,Chloroform-d)δ138.1,134.4,132.5,129.0,127.2,125.6,125.4,125.3,125.2,124. 8,48.4(d,J=2.3Hz),45.7(d,J=30.0Hz),44.1,41.5(d,J=3.2Hz),36.6(d,J=34.3Hz),34.2(d,J=10 .6Hz),33.5,33.3,28.8(d,J=10.9Hz),27.74,27.66,27.2(d,J=10.8Hz),26.9(d,J=6.0Hz),26.7( d,J=12.6Hz), 26.6(d,J=10.8Hz), 26.25(d,J=8.6Hz), 26.16, 26.0(d,J=1.4Hz), 25.9(d,J=1.4Hz).

[0129] 31 P NMR (243MHz, Chloroform-d) δ18.93 (d, J=76.5Hz).

[0130] 11 B NMR (193MHz, Chloroform-d) δ-43.26 (d, J = 58.1Hz).

[0131] HRMS(ESI)calcd for [M+Na] + :455.3009,found:455.2999.

[0132] Similar to the preparation method of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-b), 2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-e) was prepared, with the following structural formula:

[0133]

[0134] White solid, 98% yield, melting point 156℃-158℃.

[0135] 1 H NMR(600MHz,Chloroform-d)δ7.99(d,J=8.5Hz,1H),7.84(d,J=8.1Hz,1H),7.75(d,J=7.2Hz, 1H),7.67(d,J=8.1Hz,1H),7.53-7.50(m,1H),7.47-7.45(m,1H),7.42-7.40(m,1H),3.38(t,J =8.0Hz,1H),2.99-2.95(m,1H),2.57(s,1H),2.43(s,1H),1.85-1.65(m,9H),1.39-1.18(m,1 2H),0.93-0.87(m,1H),0.83-0.76(m,2H),0.36-0.29(m,1H),0.21-0.11(m,2H),0.07(s,1H).

[0136] 13C NMR(151MHz,Chloroform-d)δ139.2,134.2,132.8,128.9,126.6,125.5,125.2,125.1,124.6,124.4(d,J=9.5Hz) .,48.7(d,J=1.6Hz),47.5(d,J=19.9Hz),44.0,42.8(d,J=17.0Hz),35.9(d,J=13.1Hz),34.4(d,J=14.8Hz),33.3 1(d,J=15.5Hz),33.29,32.1(d,J=18.3Hz),31.4(d,J=15.8Hz),30.3(d,J=12.9Hz),29.5(d,J=6.1Hz),27.9,27. 8(d,J=13.7Hz), 27.7(d,J=3.9Hz), 27.4(d,J=9.1Hz), 27.1(d,J=10.5Hz), 26.6(d,J=1.1Hz), 26.5(d,J=0.8Hz).

[0137] 31 P NMR(243MHz,Chloroform-d)δ-10.04.

[0138] HRMS(ESI)calcd for [M+H] + :419.2862,found:419.2851.

[0139] Table 2: Single Crystal Test Parameters of 1-e

[0140]

[0141]

[0142] Example 6

[0143] Similar to the preparation method of 7-bromo-2-phenylbicyclo[2,2,1]heptane (2-a) in Example 1, except that iodobenzene is replaced with p-methoxyiodobenzene to prepare 7-bromo-2-(4-methoxyphenyl)bicyclo[2,2,1]heptane (2-f), the structural formula of which is as follows:

[0144]

[0145] 2-f is a colorless oily substance with a yield of 74%.

[0146] 1H NMR(600MHz,Chloroform-d)δ7.25(d,J=8.4Hz,2H),6.84(d,J=8.4Hz,2H),3.97(s,1H),3.80(s,3H),2.9 5-2.93(m,1H),2.85(s,1H),2.46-2.42(m,2H),2.04-2.00(m,1H),1.77-1.71(m,2H),1.51-1.44(m,2H).

[0147] 13 C NMR (151MHz, Chloroform-d) δ157.4,137.3,128.0,113.3,56.4,55.3,46.8,45.4,43.9,36.2,30.1,26.3.

[0148] Using 7-bromo-2-(4-methoxyphenyl)bicyclo[2,2,1]heptane (2-f) as a starting material, and employing a similar preparation method to that used for the 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphoronane adduct (3-b) in Example 2, the 2-(4-methoxyphenyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphoronane adduct (3-f) was prepared, with the following structural formula:

[0149]

[0150] White solid, yield 41%, melting point 180℃-182℃.

[0151] 1 H NMR(400MHz,Chloroform-d)δ7.30(d,J=8.1Hz,2H),6.85(d,J=8.7Hz,2H),3.77(s,3H),2.88(t,J=8.2H z,1H),2.73-2.62(m,3H),1.79-1.41(m,19H),1.26-1.12(m,4H),1.03-0.86(m,4H),0.60-0.06(m,3H).

[0152] 13C NMR(101MHz,Chloroform-d)δ157.9,135.2,129.1,113.5,55.4,48.1,45.5(d,J=2 9.8Hz), 45.4, 41.7 (d, J = 2.8Hz), 36.0 (d, J = 33.6Hz), 34.1 (d, J = 10.8Hz), 33.3 (d, J =30.2Hz),29.0(d,J=11.0Hz),28.0(d,J=21.8Hz),27.2(d,J=7.2Hz),27.08,27.0 7, 26.98 (d, J = 7.3Hz), 26.90, 26.86, 26.7 (d, J = 10.5Hz), 26.5, 26.1 (d, J = 23.9Hz).

[0153] 31 P NMR (162MHz, Chloroform-d) δ19.64 (d, J=76.0Hz).

[0154] 11 B NMR (128MHz, Chloroform-d) δ-43.40 (d, J = 59.4Hz).

[0155] HRMS(ESI)calcd for [M+Na] + :435.2959,found:435.2948.

[0156] Similar to the preparation method of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-b) in Example 2, 2-(4-methoxyphenyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-f) was prepared from the 2-(4-methoxyphenyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine borane adduct (3-f), with the following structural formula:

[0157]

[0158] White solid, 99% yield, melting point 80℃-81℃.

[0159] 1H NMR(400MHz,Chloroform-d)δ7.29(d,J=7.8Hz,2H),6.81(d,J=7.0Hz,2H),3.77(s,3H),2.77(t,J=8.0Hz,1H),2.62-2.58(m,1 H),2.47(s,1H),2.34(s,1H),1.75-1.61(m,10H),1.53-1.40(m,6H),1.27-1.19(m,6H),1.07-0.98(m,4H),0.81-0.68(m,2H).

[0160] 13 C NMR(101MHz,Chloroform-d)δ157.4,136.7,129.0,113.3,55.4,48.9(d,J=2.5Hz),47.0(d,J=1 9.9Hz),46.3,42.6(d,J=15.5Hz),35.5(d,J=13.7Hz),34.4(d,J=14.6Hz),34.0(d,J=9.5Hz),3 3.3(d,J=5.2Hz), 32.5(d,J=18.3Hz), 31.4(d,J=15.9Hz), 30.2(d,J=11.7Hz), 29.5(d,J=5.7Hz ), 28.3, 28.02 (d, J = 17.4Hz), 28.97, 27.5 (d, J = 8.6Hz), 27.3 (d, J = 10.6Hz), 26.6 (d, J = 6.9Hz).

[0161] 31 P NMR(162MHz,Chloroform-d)δ-10.00.

[0162] HRMS(ESI)calcd for [M+H] + :399.2811,found:399.2798.

[0163] Example 7

[0164] 9-Phenyl-1,2,3,4-Tetrahydro-1,4-methylenenaphthyl-2-dicyclohexylphosphine (2-g) was synthesized using a similar method to that used in Example 1 for 7-bromo-2-phenylbicyclo[2,2,1]heptane (2-a), except that bromonorbornene (4-a) was replaced with 9-bromo-1,4-dihydro-1,4-methylenenaphthalene (4-g), and the reaction in step 1 was carried out under the catalysis of 0.05 eq palladium acetate and 0.1 eq L1. The structural formula of 9-phenyl-1,2,3,4-tetrahydro-1,4-methylenenaphthyl-2-dicyclohexylphosphine (2-g) is as follows:

[0165]

[0166] Colorless liquid, yield 85%.

[0167] 1 H NMR(600MHz,Chloroform-d)δ7.47(d,J=8.2Hz,2H),7.37-7.34(m,2H),7.29-7.26(m,2H),7.24-7.21(m,1H),7.20-7.18(m,2H ),4.10(s,1H),4.04(s,1H),3.58(s,1H),3.04-3.01(m,1H),2.83(ddd,J=11.9,6.1,3.8Hz,1H),2.11(dd,J=11.9,9.2Hz,1H).

[0168] 13 C NMR (151MHz, Chloroform-d) δ146.6,144.6,143.4,128.0,126.93,126.91,125.7,121.8,120.4,57.4,52.7,50.9,44.9,31.5.

[0169] Using 9-phenyl-1,2,3,4-tetrahydro-1,4-methylenenaphthyl-2-dicyclohexylphosphine (2-g) as a starting material, the 9-phenyl-1,2,3,4-tetrahydro-1,4-methylenenaphthyl-2-dicyclohexylphosphine borane adduct (3-b) in Example 2 was prepared by a method similar to that used in Example 2:

[0170]

[0171] White solid, 58% yield, melting point 207℃-209℃.

[0172] 1H NMR(600MHz,Chloroform-d)δ7.56(d,J=8.1Hz,2H),7.35-7.36(m,2H),7.33-7.31(m,1H),7.26-7.25(m,1H),7.23-7.21(m,1H),7.16-7.11(m,2H),3.77(s,1H),3.69(s,1H),3.13(ddd,J=12.4,6.9,3.5Hz,1H),3.00(t,J=7.7Hz,1H),2.13(d,J=9.5Hz,1H),1.76-1.68(m,6H),1.63-1.46(m,8H),1.27-1.12(m,3H),1.10-0.89(m,5H),0.66-0.11(m,4H).

[0173] 13 C NMR(151MHz,Chloroform-d)δ151.1(d,J=10.4Hz),147.9(d,J=10.9Hz),141.3,129.0,128.4,126.4,126.0,125.9,121.1,119.1,55.7(d,J=23.3Hz),54.4(d,J=1.8Hz),48.6(d,J=3.4Hz),46.1,36.1(d,J=33.6Hz),32.8(d,J=29.6Hz),29.3,27.9(d,J=7.1Hz),27.1(d,J=6.2Hz),27.0(d,J=10.8Hz),26.94(d,J=1.2Hz),26.86(d,J=2.9Hz),26.6(d,J=10.8Hz),26.4,26.2(d,J=1.4Hz),25.9(d,J=1.4Hz).

[0174] 31 P NMR(243MHz,Chloroform-d)δ20.13(d,J=67.8Hz).

[0175] 11 B NMR(193MHz,Chloroform-d)δ-43.79(d,J=53.9Hz).

[0176] HRMS(ESI)calcd for[M+Na] + :453.2853,found:453.2842.

[0177] Similar to the preparation method of 2-phenylbicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-b) in Example 2, 9-phenyl-1,2,3,4-tetrahydro-1,4-methylenenaphthyl-2-dicyclohexylphosphine borane adduct (3-g) was prepared to have the following structural formula:

[0178]

[0179] White solid, 89% yield, melting point 109℃-111℃.

[0180] 1 H NMR(600MHz,Chloroform-d)δ7.54(d,J=7.7Hz,2H),7.34-7.28(m,3H),7.24-7 .23(m,1H),7.19-7.16(m,1H),7.13-7.08(m,2H),3.55(s,1H),3.43(s,1H),3. 07-3.03(m,1H),2.93(t,J=7.4Hz,1H),2.24(d,J=5.6Hz,1H),1.76-1.66(m,7H ),1.59-1.44(m,4H),1.26-1.19(m,6H),1.10-0.98(m,4H),0.78-0.72(m,2H).

[0181] 13 C NMR(151MHz,Chloroform-d)δ150.9(d,J=5.4Hz),149.2(d,J=6.1Hz),142.8,128.8(d,J=3.9Hz),128.1, 125.8,125.6,125.5,120.9,119.3,59.1(d,J=24.4Hz),55.4(d,J=3.1Hz),49.7(d,J=16.2Hz),46.4,35.3 (d,J=14.0Hz),33.7(d,J=14.8Hz),32.4(d,J=19.2Hz),31.3(d,J=16.0Hz),30.3(d,J=12.0Hz),29.3(d,J =9.5Hz), 28.2, 28.1, 28.0, 27.9 (d, J = 3.9Hz), 27.4 (d, J = 8.8Hz), 27.1 (d, J = 10.5Hz), 26.6 (d, J = 13.4Hz).

[0182] 31 P NMR(243MHz,Chloroform-d)δ-9.47.

[0183] HRMS(ESI)calcd for [M+H] + :417.2706,found:417.2693

[0184] Example 8

[0185] Resolution of the enantiomers of 2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-e):

[0186] The racemic ligand 1-e can be chirally separated by semi-preparative HPCL to obtain optically pure (+)-2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine and (-)-2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine.

[0187] The splitting condition is: Y1 5μm 250*20mm, n Hexane / i PrOH 99.5 / 0.5, 5 mL / min.

[0188] Optical rotation [α] of (+)-2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-e) D 25 =+28(c0.2,DCM).

[0189] Optical rotation [α] of (-)-2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-e) D 25 = -28(c0.2,DCM).

[0190] Using a similar method, chiral resolution can be performed on ligands 1-a to 1-d, as well as 1-f and 1-g.

[0191] Example 9

[0192] The preparation of the 1-b-Pd complex is shown in the following reaction formula:

[0193]

[0194] In a glove box, ligand 1-b (74 mg, 0.2 mmol), 2-(trimethylsilyl)ethyl 4-bromobenzoate (63 mg, 0.21 mmol), and 2 mL of dry n-hexane were added to the reaction flask. (cod)Pd(CH2TMS)2 (77 mg, 0.2 mmol) was added with stirring at room temperature. The flask was sealed and removed from the glove box, and stirring continued for 12 hours. After the reaction was complete, the mixture was filtered, and the solid was washed with n-hexane to give 117.2 mg of the product (76% yield) as a pale yellow solid.

[0195] 1 H NMR(600MHz,Chloroform-d)δ7.54-7.40(m,5H),7.36-7.33(m,3H),7.19-7.16(m,1H),4.34(s,2H),2.91(s,2H),2.29-2.20(m,2H),2.00-1.91(m,2H ),1.82-1.76(m,3H),1.68-1.64(m,4H),1.51-1.38(m,9H),1.31-1.17(m, 6H),1.09-1.07(m,4H),0.89-0.87(m,1H),0.67-0.60(m,1H),0.06(s,9H).

[0196] 13 C NMR(151MHz,Dichloromethane-d2)δ167.3,143.7,128.7,128.6,127.7,127.7,126.2,126.2,125.3,62.5,46.6,46. 0,45.7,45.6,40.8,36.3,34.3,31.6,30.95,30.86,29.7,28.9,28.8,28.7,27.6,27.0,26.5,26.1,17.2,0.8,-1.7.

[0197] 31 P NMR(243MHz,Dichloromethane-d2)δ31.16,29.36.

[0198] HRMS(ESI)calcd for [M-Br] + :695.2660,found:695.2661.

[0199] Example 10:

[0200] Suzuki coupling reaction catalyzed by 1-a ligand

[0201]

[0202] Add 1.0 mL of toluene and 0.1 mL of water to a reaction flask, then add 23 μL (2.5 x 10⁻⁶) of a pre-prepared 0.1 mg / mL Pd₂dba₃ toluene solution. -6 mmol) and 54 μL (1.5*10) of 1 mg / mL toluene solution of 1-a. -4 After stirring at room temperature for 10 minutes, phenylboronic acid (61 mg, 0.5 mmol), potassium phosphate (91 mg, 1.5 mmol), and bromobenzene (86.4 mg, 0.55 mmol) were added, and the mixture was refluxed and stirred for 12 hours. At the end of the reaction, gas chromatography showed a yield of 87% and a total number of transformations (TON) of 87,000. Under the same operating conditions, the results for other ligands were as follows: 1-b, yield 80%, TON 80,000; 1-c, yield 53%, TON 53,000; 1-d, yield 13%, TON 13,000.

[0203] The catalytic systems consisting of (+)-2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-e), (-)-2-(1-naphthyl)bicyclo[2,2,1]heptyl-7-dicyclohexylphosphine (1-e), racemic 1-e, and palladium salts all exhibit high activity in catalyzing the Suzuki coupling reaction. In addition, the catalytic systems consisting of 1-f, 1-g, and palladium salts also exhibit high activity in catalyzing the Suzuki coupling reaction.

[0204] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A norcamphorane skeleton monophosphine ligand, characterized in that, It has the following structural formula 1 or its enantiomer or racemate: in: Ar is an aryl group; R 1 R 2 The substituent is aryl or aliphatic, wherein the aliphatic substituent includes alkyl, alkenyl, or ynyl, R 1 R 2 Same or different; R 3 ~R 6 It is one or more of H, C1-C8 alkyl, C2-C8 acyloxy, hydroxyl, halogen, amino, (C1-C8 acyl)amino, di(C1-C8 alkyl)amino, C1-C8 acyl, C2-C8 ester, haloalkane, silyl, and heteroatom substituent; R 1 ~R 6 Same or different; When there are substituents in the aryl group, the substituents are one or more of the following: C1-C8 alkyl, C2-C8 acyloxy, hydroxyl, halogen, amino, (C1-C8 acyl)amino, di(C1-C8 alkyl)amino, C1-C8 acyl, C2-C8 ester, haloalkane, silyl, heteroatom substituents; the number of substituents is 0-5.

2. The norcamphorane skeleton monophosphine ligand as described in claim 1, characterized in that, The C1-C8 alkyl group is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, sec-octyl, or tert-octyl. The C1-C8 acyl groups are formyl, acetyl, propionyl, n-butyryl, isobutyryl, n-valeryl, isovaleryl, sec-valeryl, neovaleryl, n-hexanoyl, isohexanoyl, neohexanoyl, sec-hexanoyl, n-heptanoyl, isoheptanoyl, neoheptanoyl, sec-heptanoyl, n-octanoyl, isooctanoyl, neoctanoyl, sec-octanoyl, 1-cyclopropylformyl, 1-cyclobutylformyl, 1-cyclopentylformyl, 1-cyclohexylformyl, 1-cycloheptylformyl; The C2-C8 acyloxy groups are acetyloxy, propionyloxy, n-butyryloxy, isobutyryloxy, n-valeryloxy, isovaleryloxy, sec-valeryloxy, neovaleryloxy, n-hexanoyloxy, isohexanoyloxy, neohexanoyloxy, sec-hexanoyloxy, n-heptanoyloxy, isoheptanoyloxy, neoheptanoyloxy, sec-heptanoyloxy, n-octanoyloxy, isooctanoyloxy, neoctanoyloxy, sec-octanoyloxy, 1-cyclopropylformyloxy, 1-cyclobutylformyloxy, 1-cyclopentylformyloxy, 1-cyclohexylformyloxy, 1-cycloheptylformyloxy; The C2-C8 ester groups are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, secondary pentoxycarbonyl, tertiary pentoxycarbonyl, cyclopentoxycarbonyl, n-hexyloxycarbonyl, isohexyloxycarbonyl, neohexyloxycarbonyl, secondary hexyloxycarbonyl, tertiary hexyloxycarbonyl, cyclohexyloxycarbonyl, n-heptoxycarbonyl, isoheptoxycarbonyl, neoheptoxycarbonyl, secondary hexyloxycarbonyl, tertiary hexyloxycarbonyl, and cycloheptoxycarbonyl.

3. The norcamphorane skeleton monophosphine ligand as described in claim 1, characterized in that, It has the following structural formulas: 1-a, 1-b, 1-c, 1-d, 1-e, 1-f, or 1-g, or the enantiomers and racemates of the following structural formulas:

4. The method for preparing the norcamphorane skeleton monophosphine ligand according to any one of claims 1-3, characterized in that, Includes the following steps: Step 1: Using a palladium metal complex as a catalyst and triethylamine and formic acid as negative hydrogen sources, in a solvent, bromonorbornene and its analogues, as shown in formula 4, undergo a hydroarylation reaction with ArX, where X in ArX is I, Br, or OTf, to prepare an aryl-substituted bromonorbornene skeleton, as shown in formula 2. The reaction formula is as follows: Step 2: After the aryl-substituted bromonorbornene skeleton of structure 2 undergoes a bromide-lithium exchange with tert-butyllithium, it is then reacted with R... 1 R 2 PCl undergoes a substitution reaction to prepare the norcamphorane skeleton monophosphine ligand as shown in Formula 1, as follows:

5. The adduct of the norbornene skeleton monophosphine ligand and borane as described in any one of claims 1-3, characterized in that, It has the following 3 structural formulas, or enantiomers and racemates of the following 3 structural formulas:

6. The method for preparing the adduct as described in claim 5, characterized in that, The steps are as follows: A norunane skeleton monophosphine ligand with structural formula 1 reacts with a tetrahydrofuran solution of borane to generate the corresponding adduct with structural formula 3, and the reaction formula is as follows: Alternatively, the aryl-substituted bromonorbornene skeleton of structure 2 can undergo bromolithium exchange with tert-butyllithium, followed by R. 1 R 2 PCl undergoes a substitution reaction, followed by the addition of a tetrahydrofuran solution of borane to prepare an adduct with the structural formula shown in Figure 3. The reaction formula is as follows:

7. A palladium complex based on the norbornene skeleton monophosphine ligand as described in any one of claims 1-3, characterized in that, Having the following 5 structural formulas, or enantiomers or racemates of the following 5 structural formulas: X and Y are halogens, acid radicals, 1,3-dicarbonyl ligands, allyl or aryl groups, and X and Y may be the same or different.

8. The method for preparing the palladium complex according to claim 7, characterized in that, Includes the following steps: The palladium complex is obtained by reacting the norcamphor skeleton monophosphine ligand, or the norcamphor skeleton monophosphine ligand and borane adduct, with palladium salt and XY in a solvent and then separating and purifying them. Preferably, the palladium salt is one or more of (COD)Pd(CH2TMS)2, Pd2(dba)3.CHCl3, Pd2(dba)4, Pd(OAc)2, Pd(TFA)2 or [(allyl)PdCl]2.

9. The application of the palladium complex as described in claim 8 as a catalyst in the catalytic Suzuki coupling reaction.

10. The application of the norcamphor skeleton monophosphine ligand as described in claim 1, or the adduct of the norcamphor skeleton monophosphine ligand and borane with palladium salt, as a catalytic system in the catalytic Suzuki coupling reaction.

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