Synthesis method of trisubstituted phosphine and oxygen / sulfur / boride thereof

Abstract

The invention belongs to the technical field of synthetic chemistry, and particularly relates to a synthetic method of trisubstituted phosphine and oxygen / sulfur / boride thereof. According to the method, halogenated hydrocarbon and a diaryl / alkyl phosphine compound are taken as reaction substrates, the trisubstituted phosphine is prepared through direct one-step reaction without any other catalyst, additive or solvent, and the oxygen / sulfur / boride of the trisubstituted phosphine is obtained through further simple conversion. The synthesis method disclosed by the invention is green and environment-friendly, efficient in reaction, cheap and easily available in raw materials, simple to operate, good in atom economy, good in substrate applicability and high in yield. The efficiently synthesized trisubstituted phosphine and the oxygen / sulfur / boride thereof are important skeletons of many drugs, bioactive molecules and natural products. The synthesis method provided by the invention provides a widely applicable preparation method for synthesis of the compounds.

Description

Technical Field

[0001] The invention belongs to the technical field of synthetic chemistry, and particularly relates to a method for synthesizing a trisubstituted phosphine and its oxygen / sulfur / boride. Background Art

[0002] Asymmetric tertiary phosphines are highly effective catalyst ligands used in organic synthesis, attracting considerable attention for their synthesis and development. As ligands, trivalent phosphines can coordinate with transition metals and, through modification of substituents on the phosphorus atom, modulate electronic and steric properties, effectively enhancing the reactivity and selectivity of metal catalysts and aiding the construction of complex organic molecules. Furthermore, trivalent phosphine backbones can be transformed into corresponding phosphine-oxygen / sulfur / boron compounds through a simple one-step conversion, making them important research targets in organic chemistry, medicinal chemistry, pesticides, and other fields.

[0003] The classical synthesis method of trisubstituted phosphines is mainly achieved by the reaction of organometallic reagents and phosphine halides (Zhang, M.; Ma, Z.; Du, H. Wang, Z. Tetrahedron Lett. 2020, 61 (28), 152125), or by reacting metal phosphines with halogenated hydrocarbons to generate the corresponding trisubstituted phosphines (Wolfe, B.; Livinghouse, TJAm. Chem. Soc. 1998, 120 (20), 5116-5117). These methods require stoichiometric amounts of air-unstable metal compounds as substrates, which limits their application. In recent years, transition metal-catalyzed PC bond cross-coupling has made great progress and is a very promising P(III)-C(sp 3) bond construction method. In 2007, Paolo Melchiorre and his team used a bifunctional cinchona alkaloid catalyst to achieve the enantioselective addition of diphenylphosphine to a series of nitroolefins (Bartoli, G.; Bosco, M.; Carlone, A.; Locatelli, M.; Mazzanti, A.; Sambri, L.; Melchiorre, P. Chem. Commun. 2007, No. 7, 722-724). David S. Glueck and his team completed the platinum-catalyzed hydrophosphination reaction of activated olefins in 2005 (Scriban, C.; Kovacik, I.; Glueck, DS Organometallics. 2005, 24 (21), 4871-4874). In 2020, Liang Yin successfully achieved the synthesis of asymmetric diaryl phosphines through copper (I)-catalyzed conjugate addition of α, β-unsaturated amides, and obtained chiral phosphine compounds with diastereoselectivity and enantioselectivity respectively (Li, Y.-B.; Tian, ​​H.; Yin, L. Am. Chem. Soc. 2020, 142(47), 20098-20106).

[0004] Although there are many methods for synthesizing trisubstituted phosphines, C(sp 3 )-P(III) bond construction method is still a technical challenge that needs to be overcome.

[0005] Therefore, a green method for synthesizing trisubstituted phosphines using aryl halides and PH compounds as substrates is needed to be developed without solvents, catalysts, or any additives. The reaction has good functional group tolerance and can obtain the target compound in moderate to excellent yields. Summary of the Invention

[0006] In response to the problem that the synthesis methods of trisubstituted phosphines and their oxygen / sulfur / boride compounds are not efficient and green enough, a solvent-free, catalyst-free, green and efficient synthesis method has been developed.

[0007] The present invention provides a method for synthesizing a trisubstituted phosphine and its oxygen / sulfur / boride. The synthesis method comprises the following steps: mixing a raw material halide and a diaryl / alkyl phosphine, reacting the mixture under an inert gas atmosphere until the raw material disappears, and then further oxidizing / sulfurizing / boranizing the mixture, followed by separation and purification to obtain the trisubstituted phosphine oxygen / sulfur / boride. The reaction formula of the synthesis method is shown in Formula I below:

[0008]

[0009] In formula I, X is Br or I; R 1is selected from benzene and its substituents, naphthyl, 3-8 C cycloalkyl and its substituents; said R 1 The substituents of the benzene substituent are selected from 1-8 C alkyl, 1-8 C alkenyl, halogen, 1-8 C haloalkyl, 1-8 C alkoxy, 1-8 C haloalkoxy, the number is 1-4, and the position is any position of the benzene ring; the R 1 The substituent of the cycloalkyl substituent is selected from 1-8 C alkyl, 1-8 C alkenyl, and halogen;

[0010] R 2 is selected from benzene and its substituents, 1-8 C alkyl, 3-8 C cycloalkyl; said R 2 The substituents of the benzene substituent are selected from 1-8 C alkyl and 3-8 C alkoxy, the number is 1-4, and the position is any position of the benzene ring.

[0011] Preferably, the R 1 One selected from phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-trifluoromethylphenyl, p-trifluoromethoxyphenyl, 3,4-difluorophenyl, 2,6-dichlorophenyl, 2-fluoro-6-chlorophenyl, 2-fluoro-4-ethoxy-6-chlorophenyl, 2,3,4-trifluorophenyl, naphthyl, 4,4-difluorocyclohexyl, styryl, cyclopropylmethyl, benzyl, and phenethyl.

[0012] Preferably, the R 2 One selected from phenyl, p-methylphenyl, 2-methoxyphenyl, isopropyl, tert-butyl and cyclohexyl.

[0013] Preferably, the molar ratio of the halide to the diaryl / alkyl phosphine compound is 1 to 1.1:1.

[0014] Preferably, the reaction temperature is room temperature to 100°C.

[0015] Preferably, the reaction time is 10 to 72 hours.

[0016] Preferably, the oxidation method is contact with oxygen.

[0017] Preferably, the sulfurization method is to react with S8.

[0018] Preferably, the boranylation method is a BH3·SMe2 reaction.

[0019] Preferably, the trisubstituted phosphine and its oxygen / sulfur / boride specifically include the following compounds:

[0020]

[0021]

[0022] The present invention has the following advantages: Using bromo / iodo hydrocarbons and diaryl / alkyl phosphines as substrates, the present invention can produce trisubstituted phosphines in high yields and convert them into their oxygen / sulfur / boride compounds without the addition of any catalysts, additives, or solvents. Depending on the substrate, the reaction can be performed at room temperature to 100°C for 10 to 72 hours. Compared to existing technologies, the present invention's synthesis method has the following advantages:

[0023] (1) The present invention uses bromine / iodine hydrocarbons and diaryl / alkyl phosphines as substrates, which are stable in nature and widely available;

[0024] (2) The method of the present invention does not require the addition of any catalyst, additive, solvent, etc., and the reaction process is green;

[0025] (3) The synthesis method of the present invention can prepare trisubstituted phosphines, trisubstituted phosphine oxides, trisubstituted phosphine sulfides, and trisubstituted phosphine borides in a simple and efficient manner;

[0026] (4) The synthesis method of the present invention has high yield and a wide range of substrate applications;

[0027] (5) The synthesis method of the present invention can be fed in a 1:1 ratio, has no other by-products, and has good atom economy.

[0028] The trisubstituted phosphine and its oxygen / sulfur / boride synthesized efficiently in the present invention are important skeletons of many drugs and bioactive molecules. The synthesis method of the present invention provides a widely applicable preparation method for the synthesis of such compounds. DETAILED DESCRIPTION

[0029] Example 1

[0030] Synthesis of (3a) using benzyl bromide (1a) and diphenylphosphine (2a) as raw materials:

[0031]

[0032] 0.3 mmol of benzyl bromide (1a) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting materials disappeared completely (about 10 hours). After the reaction, 2 mL of tetrahydrofuran was added to the system, filtered, and washed to obtain a white solid 3a in 88% yield.

[0033] 1 H NMR (300MHz, Chloroform-d) δ7.75–7.62(m,4H),7.47(dd,J=16.1,6.2Hz,6H),7.14(d,J=17.5Hz,5H),3.66(d,J=13.7Hz,2H).13 C NMR (75MHz, Chloroform-d) δ134.76 (d, J = 3.0Hz), 133.93 (d, J = 10.1Hz), 130.37 (d, J = 6.2Hz), 130.01 (d, J = 12.7 Hz), 129.25 (d, J = 3.1Hz), 128.44 (d, J = 3.8Hz), 127.59 (d, J = 8.2Hz), 116.25 (d, J = 80.3Hz), 28.88 (d, J = 44.7Hz). 31 P NMR(121MHz,Chloroform-d)δ1.47.

[0034] Example 2

[0035] Synthesis of (4a) using benzyl bromide (1a) and diphenylphosphine (2a) as raw materials:

[0036]

[0037] 0.3 mmol of benzyl bromide (1a) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4a. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and column chromatography was performed using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 93% yield.

[0038] 1 H NMR(300MHz,Chloroform-d)δ7.99–7.89(m,4H),7.60(dd,J=8.5,6.5Hz,2H),7.46(td ,J=7.6,3.2Hz,4H),7.38–7.33(m,2H),7.12(d,J=6.8Hz,3H),4.53(d,J=15.5Hz,2H). 13 CNMR(75MHz,Chloroform-d)δ132.81,131.96(d,J=2.7Hz),131.29(d,J=31.4Hz),131.29(d,J =9.2Hz), 130.25 (d, J = 5.3Hz), 128.74–128.33 (m), 126.90 (d, J = 3.0Hz), 38.15 (d, J = 66.4Hz). 31 P NMR(121MHz,Chloroform-d)δ29.82.

[0039] Example 3

[0040] Synthesis of (4b) using 2-methylbenzyl bromide (1b) and diphenylphosphine (2a) as raw materials:

[0041]

[0042] 0.3 mmol of 2-methylbenzyl bromide (1b) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4b. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and column chromatography was performed using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 93% yield.

[0043] 1 H NMR (300MHz, Chloroform-d) δ7.72–7.62(m,4H),7.56–7.40(m,7H),7.08(d,J=3.6Hz,2H),7.02–6.93(m,2H),3.67(d,J=14.0Hz,2H),2.14(s,3H). 13 C NMR(75MHz,Chloroform-d)δ137.58(d,J=5.4Hz),133.07,132.00(d,J=2.7Hz),131.76,131.35(d,J=9.1Hz),131.11–130.34(m) ,129.70(d,J=8.1Hz), 128.61(d,J=11.6Hz), 127.13(d,J=3.2Hz), 125.88(d,J=2.9Hz), 35.32(d,J=66.7Hz), 20.18(d,J=1.0Hz). 31 P NMR(121MHz,Chloroform-d)δ29.65.

[0044] Example 4

[0045] Synthesis of (4c) using 3-methylbenzyl bromide (1c) and diphenylphosphine (2a) as raw materials:

[0046]

[0047] 0.33 mmol of 3-methylbenzyl bromide (1c) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material disappeared completely (10 hours). The mixture was left open to air for 5 hours to obtain 4c. The mixture was extracted three times with ethyl acetate and saturated aqueous sodium carbonate. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 95% yield.

[0048] 1 H NMR(300MHz,Chloroform-d)δ7.80–7.64(m,4H),7.59–7.36(m,6H),7.05(t,J=7.5Hz ,1H),6.99–6.90(m,2H),6.86(d,J=7.4Hz,1H),3.60(d,J=13.7Hz,2H),2.20(s,3H). 13 CNMR(75MHz,Chloroform-d)δ137.92(d,J=2.6Hz),133.03,131.92–131.62(m),131.19(d,J=9.1Hz),131.01(d,J=1.4Hz),130.99(d,J=11. 7Hz), 128.46 (d, J = 11.7Hz), 128.20 (d, J = 2.5Hz), 127.55 (d, J = 3.0Hz), 127.12 (d, J = 5.3Hz), 81.12–74.59 (m), 38.06 (d, J = 66.6Hz), 21.33. 31 P NMR(121MHz,Chloroform-d)δ29.48.

[0049] Example 5

[0050] Compound (4d) was synthesized from 4-methylbenzyl bromide (1d) and diphenylphosphine (2a):

[0051]

[0052] 0.33 mmol of 4-methylbenzyl bromide (1d) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4d. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 1:1 to obtain a white solid in a 90% yield.

[0053] 1 H NMR (300MHz, Chloroform-d) δ7.74–7.65(m,4H),7.54–7.39(m,6H),6.99(s,4H),3.61(d,J=13.6Hz,2H),2.25(d,J=1.7Hz,3H). 13C NMR(75MHz,Chloroform-d)δ136.43(d,J=3.1Hz),133.09,131.81(d,J=2.8Hz),131.23(d,J=9.1Hz),130.03 (d, J=5.2Hz), 129.17 (d, J=2.5Hz), 128.53 (d, J=11.6Hz), 127.91 (d, J=8.0Hz), 37.66 (d, J=66.9Hz), 21.12. 31 P NMR(121MHz,Chloroform-d)δ29.51.

[0054] Example 6

[0055] Compound (4e) was synthesized from 2-fluorobenzyl bromide (1e) and diphenylphosphine (2a):

[0056]

[0057] 0.33 mmol of 2-fluorobenzyl bromide (1e) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material disappeared completely (10 hours). The mixture was left open to air for 5 hours to obtain 4e. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 96% yield.

[0058] 1 H NMR(300MHz,Chloroform-d)δ7.76–7.66(m,4H),7.53–7.38(m,7H),7.19–7.0 7(m,1H),7.01(t,J=7.3Hz,1H),6.86(t,J=9.1Hz,1H),3.69(d,J=13.7Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ160.60(dd,J=245.7,6.2Hz),132.80,132.16(t),131.96(d,J=2.8Hz),131.4 8,131.06(d,J=9.3Hz),128.55(dd),124.19(t),118.68(dd,J=15.3,7.7Hz),115.18(dd,J=22.3,2.4Hz). 31 P NMR(121MHz,Chloroform-d)δ29.53. 19 F NMR(282MHz,Chloroform-d)δ-117.02–-117.15(m).

[0059] Example 7

[0060] Synthesis of (4f) using 3-fluorobenzyl bromide (1f) and diphenylphosphine (2a) as raw materials:

[0061]

[0062] 0.33 mmol of 3-fluorobenzyl bromide (1f) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material disappeared completely (10 hours). The mixture was left open to air for 5 hours to obtain 4f. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 95% yield.

[0063] 1 H NMR (300MHz, Chloroform-d) δ7.80–7.63(m,4H),7.56–7.37(m,6H),7.26(s,1H),7.13(q,J=7.8Hz,0H),6.95–6.77(m,3H),3.63(d,J=13.7Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ162.58(dd,J=245.9,2.8Hz),133.67(t,J=8.0Hz),132.68,132.05(d,J=2.7Hz),131.50–130.83(m),129.82(dd,J=8 .4, 2.6Hz), 128.66 (d, J = 11.8Hz), 125.94 (dd, J = 5.3, 2.9Hz), 117.12 (dd, J = 22.0, 5.2Hz), 113.87 (dd, J = 21.0, 2.9Hz), 37.93 (dd, J = 66.0, 1.7Hz). 31 PNMR(121MHz,Chloroform-d)δ29.20. 19 F NMR(282MHz,Chloroform-d)δ-108.34–-116.64(m).

[0064] Example 8

[0065] Synthesized from 4-fluorobenzyl bromide (1g) and diphenylphosphine (2a) (4g):

[0066]

[0067] 0.33 mmol of 4-fluorobenzyl bromide (1 g) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4 g. The mixture was extracted three times with ethyl acetate and saturated sodium carbonate solution. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 1:1 to obtain a white solid in a yield of 96%.

[0068] 1 H NMR (300MHz, Chloroform-d) δ7.74–7.61(m,4H),7.54–7.38(m,6H),7.13–6.98(m,2H),6.86(t,J=8.6Hz,2H),3.60(d,J=13.3Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ161.95(dd,J=245.3,3.2Hz),132.06(d,J=99.3Hz),132.00(d,J=2.7Hz),131.64(dd,J=8.0,5 .2Hz), 131.17 (d, J = 9.2Hz), 128.65 (d, J = 11.7Hz), 126.86 (dd, J = 8.0, 3.2Hz), 115.36 (d, J = 23.9Hz), 37.23 (d, J = 66.8Hz). 31 P NMR(121MHz,Chloroform-d)δ29.52. 19 FNMR(282MHz,Chloroform-d)δ-115.89(tt,J=10.0,5.0Hz).

[0069] Example 9

[0070] Synthesized from 2-chlorobenzyl bromide (1h) and diphenylphosphine (2a) (4h):

[0071]

[0072] 0.33 mmol of 2-chlorobenzyl bromide (1h) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4h. The mixture was extracted three times with ethyl acetate and saturated sodium carbonate solution. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 1:1 to obtain a white solid in an 83% yield.

[0073] 1H NMR (300MHz, Chloroform-d) δ7.75–7.65(m,4H),7.55–7.36(m,7H),7.14(ddt,J=16.5,14.6,7.2Hz,3H),3.85(d,J=13.9Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ134.31(d,J=7.0Hz),132.75,131.99(t,J=3.6Hz),131.43,131.15(d,J=9.3Hz),129.72(d ,J=7.4Hz), 129.42(d,J=2.3Hz), 128.52(d,J=11.8Hz), 128.31(d,J=2.8Hz), 126.87(d,J=2.6Hz), 34.61(d,J=66.6Hz). 31 P NMR(121MHz,Chloroform-d)δ29.55.

[0074] Example 10

[0075] Compound (4i) was synthesized from 3-chlorobenzyl bromide (1i) and diphenylphosphine (2a):

[0076]

[0077] 0.33 mmol of 3-chlorobenzyl bromide (1i) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material disappeared completely (10 hours). The mixture was left open to air for 5 hours to obtain 4i. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 90% yield.

[0078] 1 H NMR (300MHz, Chloroform-d) δ7.74–7.62(m,4H),7.45(dtd,J=14.3,7.0,2.2Hz,6H),7.20–6.97(m,4H),3.59(d,J=13.6Hz,2H). 13C NMR(75MHz,Chloroform-d)δ134.05(d,J=2.9Hz),133.28(d,J=7.9Hz),132.58,132.04(d,J=2.8Hz),131.31–130.93(m),130 .15(d,J=5.3Hz), 129.58(d,J=2.6Hz), 128.63(d,J=11.8Hz), 128.34(d,J=5.1Hz), 127.05(d,J=3.0Hz), 37.82(d,J=65.8Hz). 31 P NMR(121MHz,Chloroform-d)δ29.12.

[0079] Example 11

[0080] Synthesis of (4j) using 4-chlorobenzyl bromide (1j) and diphenylphosphine (2a) as raw materials:

[0081]

[0082] 0.33 mmol of 4-chlorobenzyl bromide (1j) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4j. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in an 82% yield.

[0083] 1 H NMR (300MHz, Chloroform-d) δ7.75–7.61(m,4H),7.57–7.37(m,6H),7.15(d,J=8.2Hz,2H),7.07–6.99(m,2H),3.61(d,J=13.5Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ132.94(d,J=3.6Hz),132.73,132.08(d,J=2.8Hz),131.57–131.39( m), 131.21 (d, J = 9.2Hz), 129.81 (d, J = 8.0Hz), 128.80, 128.65 (d, J = 2.3Hz), 37.57 (d, J = 66.2Hz). 31 P NMR(121MHz,Chloroform-d)δ29.17

[0084] Example 12

[0085] Synthesis (4k) using 2-trifluoromethylbenzyl bromide (1k) and diphenylphosphine (2a) as raw materials:

[0086]

[0087] 0.33 mmol of 2-trifluoromethylbenzyl bromide (1k) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4k. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in an 87% yield.

[0088] 1 H NMR (300MHz, Chloroform-d) δ7.60(d,J=8.1Hz,1H),7.41(d,1H),7.38(dd,J=3.4,1.4Hz,2H),7.35(d,J=1.5Hz,1H),7.23(s,1H),7.20(d,J=1. 5Hz,1H),7.17(d,J=1.5Hz,1H),7.14(d,J=2.9Hz,2H),7.12(d,J=2.9Hz,2H),7.11–7.09(m,1H),6.99(t,J=7.4Hz,1H),3.57(d,J=14.2Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ132.70,132.32(d,J=4.9Hz),132.07(d,J=2.8Hz),131.90,131.37,130.70(dd ,J=7.1,1.6Hz),128.63(d,J=11.9Hz),127.23–126.90(m),126.48–125.89(m),34.16(dd,J=66.8,1.8Hz). 31 P NMR(121MHz,Chloroform-d)δ29.73. 19 F NMR(282MHz,Chloroform-d)δ-58.94.

[0089] Example 13

[0090] Synthesis of (4l) using 4-trifluoromethoxybenzyl bromide (1l) and diphenylphosphine (2a) as raw materials:

[0091]

[0092] 0.33 mmol of 4-trifluoromethoxybenzyl bromide (1L) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4L. The mixture was extracted three times with ethyl acetate and saturated aqueous sodium carbonate solution. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 1:1 to obtain a white solid in a 90% yield.

[0093] 1 H NMR(300MHz,Chloroform-d)δ7.70(d,J=1.2Hz,1H),7.67(dd,J=3.3,1.4Hz,2H),7.63(d,J=1.6Hz,1H),7.53 –7.46(m,2H),7.45–7.39(m,4H),7.11(dd,J=8.7,2.1Hz,2H),7.00(d,J=8.6Hz,2H),3.62(d,J=13.4Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ148.18,132.54,132.07(d,J=2.8Hz),131.45(d,J=5.1Hz),131 .20(d,J=3.8Hz),131.05,130.05(d,J=8.1Hz),128.66(d,J=11.8Hz),37.38(d,J=66.1Hz). 31 P NMR(121MHz,Chloroform-d)δ29.44. 19 F NMR(282MHz,Chloroform-d)δ-57.88.

[0094] Example 14

[0095] Synthesize (4m) from 3,4-difluorobenzyl bromide (1m) and diphenylphosphine (2a):

[0096]

[0097] 0.33 mmol 3,4-difluorobenzyl bromide (1 m) and 0.3 mmol diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4 m. The mixture was extracted three times with ethyl acetate and saturated sodium carbonate solution. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 1:1 to obtain a white solid in an 88% yield.

[0098] 1H NMR(300MHz,Chloroform-d)δ7.70(s,1H),7.66(dd,J=3.4,1.4Hz,2H),7.63(d,J=1.6Hz,1H),7.47(dd,J=7.2,1.5 Hz,2H),7.41(td,J=7.1,3.0Hz,4H),6.92(q,J=8.4,8.0Hz,2H),6.79(q,J=5.0,3.2Hz,1H),3.56(d,J=13.3Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ151.32(ddd,J=35.3,12.6,3.0Hz),148.08(ddd),132.40,132.10(d,J=2.8Hz),131.01(d,J=9.3Hz),128.67(d,J=11 .8Hz), 128.19 (ddd, J=8.0, 6.3, 4.0Hz), 126.16 (td, J=5.8, 3.7Hz), 118.96 (dd, J=17.8, 5.0Hz), 117.06 (dd, J=17.2, 2.2Hz), 37.11 (d, J=67.3Hz). 31 P NMR(121MHz,Chloroform-d)δ29.18–29.09(m). 19 F NMR(282MHz,Chloroform-d)δ-137.44–-137.81(m),-140.40(dddd,J=22.0,12.1,9.9,4.7Hz).

[0099] Example 15

[0100] Synthesis (4n) from 2,5-dichlorobenzyl bromide (1n) and diphenylphosphine (2a):

[0101]

[0102] 0.33 mmol of 2,5-dichlorobenzyl bromide (1n) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4n. Ethyl acetate and saturated aqueous sodium carbonate solution were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 1:1 to obtain a white solid in an 80% yield.

[0103] 1H NMR(300MHz,Chloroform-d)δ7.72(d,J=1.2Hz,1H),7.69(dd,J=3.4,1.4Hz,2H),7.66(d,J=1.5H z,1H),7.50(td,J=7.3,1.5Hz,2H),7.45–7.38(m,5H),7.16–7.03(m,2H),3.79(d,J=13.8Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ132.61(d,J=11.5Hz),132.58(d,J=1.5Hz),132.39,132.16(d,J=2.8Hz),131.72(d,J=4.3Hz),13 1.53(d,J=7.6Hz), 131.11(d,J=9.4Hz), 130.37(d,J=2.3Hz), 128.63(d,J=11.9Hz), 128.44(d,J=2.8Hz), 34.72(d,J=65.6Hz). 31 P NMR(121MHz,Chloroform-d)δ29.13.

[0104] Example 16

[0105] Synthesis of (4o) using 2-chloro-6-fluorobenzyl bromide (1o) and diphenylphosphine (2a) as raw materials:

[0106]

[0107] 0.33 mmol of 2-chloro-6-fluorobenzyl bromide (1o) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4o. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in an 87% yield.

[0108] 1 H NMR(300MHz,Chloroform-d)δ7.76(s,1H),7.75–7.72(m,2H),7.70(d,J=1.4Hz,1H),7.51(td,J=7.3 ,1.4Hz,2H),7.46–7.39(m,4H),7.12–7.06(m,2H),6.90–6.81(m,1H),3.91(dd,J=13.6,1.7Hz,2H). 13C NMR(75MHz,Chloroform-d)δ161.36(dd,J=249.9,5.0Hz),135.87(t,J=5.3Hz),132.94,132.02(d,J=2.8Hz),131.62,131.24(d,J =9.4Hz), 129.07–128.28(m), 125.38(t,J=3.1Hz), 118.90(dd,J=18.7,8.7Hz), 113.95(dd,J=22.7,2.8Hz), 30.33(d,J=65.7Hz). 31 P NMR(121MHz,Chloroform-d)δ27.78. 19 FNMR(282MHz,Chloroform-d)δ-101.86–-119.01(m).

[0109] Example 17

[0110] Synthesize (4p) from 2-chloro-4-ethoxy-6-fluorobenzyl bromide (1p) and diphenylphosphine (2a):

[0111]

[0112] 0.33 mmol of 2-chloro-4-ethoxy-6-fluorobenzyl bromide (1o) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4o. Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in a 92% yield.

[0113] 1 H NMR(300MHz,Chloroform-d)δ7.79–7.70(m,4H),7.52(td,J=7.3,1.5Hz,2H),7.44(td,J=7.2,2.9H z, 4H), 6.32 (d, J = 9.3Hz, 2H), 3.92 (q, J = 7.0Hz, 2H), 3.64 (d, J = 13.0Hz, 2H), 1.36 (t, J = 7.0Hz, 3H). 13C NMR(75MHz,Chloroform-d)δ163.44(dd,J=11.1,4.7Hz),160.40–158.84(m),132.28(d,J=99.2Hz), 131.99(d,J=2.8Hz), 131.26(d,J=9.3Hz), 128.50(d,J=11.8Hz), 64.21, 25.88(d,J=68.0Hz), 14.62. 31 P NMR(121MHz,Chloroform-d)δ27.95. 19 F NMR (282MHz, Chloroform-d) δ-111.26 (d, J = 10.2Hz).

[0114] Example 18

[0115] Synthesis (4q) from 2,3,4-trifluorobenzyl bromide (1q) and diphenylphosphine (2a):

[0116]

[0117] 0.33 mmol of 2,3,4-trifluorobenzyl bromide (1q) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at room temperature until the starting material completely disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4q. The mixture was extracted three times with ethyl acetate and saturated aqueous sodium carbonate. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in an 87% yield.

[0118] 1 H NMR(300MHz,Chloroform-d)δ7.71(ddd,J=11.7,8.2,1.5Hz,4H),7.60–7.40(m,6 H),7.22–7.09(m,1H),6.85(tdd,J=9.3,7.1,2.1Hz,1H),3.64(d,J=13.2Hz,2H). 13CNMR(75MHz,Chloroform-d)δ152.39–150.81(m),148.97–147.64(m),141.48(td,J=15.7,2.7Hz),138.16(td,J=15.6,2.5Hz),133.16–1 31.98 (m), 130.97 (d, J = 9.4Hz), 128.85, 125.44 (dq, J = 8.1, 4.3Hz), 117.04–115.98 (m), 112.17 (dt, J = 17.4, 3.3Hz), 29.81 (d, J = 67.0Hz). 31 P NMR(121MHz,Chloroform-d)δ28.93. 19 F NMR(282MHz,Chloroform-d)δ-135.80(ddt,J=20.9,9.6,5.7Hz),-137.05(dd,J=18.7,8.2Hz),-159.09–-160.52(m).

[0119] Example 19

[0120] Synthesis of (4r) using 2-bromomethylnaphthalene (1r) and diphenylphosphine (2a) as raw materials:

[0121]

[0122] 0.33 mmol of 2-bromomethylnaphthalene (1r) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a nitrogen atmosphere at 30°C until the starting material disappeared (10 hours). The mixture was left open to air for 5 hours to obtain 4r. The mixture was extracted three times with ethyl acetate and saturated sodium carbonate solution. The organic phases were combined, concentrated in vacuo, and purified by column chromatography using a 1:1 ratio of n-hexane to ethyl acetate to afford a white solid in an 86% yield.

[0123] 1 H NMR (300MHz, Chloroform-d) δ7.78–7.65(m,7H),7.57(s,1H),7.54–7.39(m,8H),7.23(d,J=8.5Hz,1H),3.82(d,J=13.8Hz,2H). 13C NMR(75MHz,Chloroform-d)δ133.39(d,J=2.6Hz),133.05,132.32(d,J=2.1Hz),13 1.96(d,J=2.7Hz),131.73,131.31(d,J=9.1Hz),129.11(d,J=6.7Hz),128.87(d,J =8.2Hz),128.64(d,J=11.7Hz),128.30(d,J=4.2Hz),128.06(d,J=2.0Hz),127.71 (dd,J=6.4,1.0Hz),126.18–125.91(m),125.77(d,J=1.1Hz),38.47(d,J=66.4Hz). 31 P NMR(121MHz,Chloroform-d)δ29.42.

[0124] Example 20

[0125] Synthesis of (5a) using benzyl bromide (1a) and diphenylphosphine (2a) as raw materials:

[0126]

[0127] 0.33 mmol of benzyl bromide (1a) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5a. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 92%.

[0128] 1 H NMR(300MHz,Chloroform-d)δ7.98–7.71(m,4H),7.46(dddd,J=14.3,9.7,4.3,1 .7Hz,6H),7.17(q,J=8.7,7.4Hz,3H),7.03–6.97(m,2H),3.85(d,J=13.5Hz,2H). 13CNMR(75MHz,Chloroform-d)δ132.74,131.74,131.63(d,J=3.7Hz),130.84(d,J=7.5Hz),130.56(d , J=5.3Hz), 128.56 (d, J=12.0Hz), 128.02 (d, J=3.2Hz), 127.20 (d, J=3.7Hz), 40.96 (d, J=50.6Hz). 31 P NMR(121MHz,Chloroform-d)δ42.18.

[0129] Example 21

[0130] Synthesis of (5b) using 2-methylbenzyl bromide (1b) and diphenylphosphine (2a) as raw materials:

[0131]

[0132] 0.33 mmol of 2-methylbenzyl bromide (1b) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5b. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 90%.

[0133] 1 H NMR(300MHz,Chloroform-d)δ7.87–7.73(m,4H),7.59–7.39(m,6H),7.12(dt,J=12.1,6.9 Hz,2H),7.00(t,J=7.6Hz,1H),6.90(d,J=7.9Hz,1H),3.92(d,J=13.8Hz,2H),2.05(s,3H). 13 C NMR(75MHz,Chloroform-d)δ137.77(d,J=5.8Hz),132.87,131.82,131.68(d,J=9.8Hz),130.77(d,J=4.9Hz),130.40(d,J=3.1Hz),1 29.57(d,J=7.8Hz),128.48(d,J=12.0Hz),127.30(d,J=3.7Hz),125.44(d,J=3.4Hz),81.55–74.03(m),37.85(d,J=50.8Hz),20.20. 31P NMR(121MHz,Chloroform-d)δ41.44.

[0134] Example 22

[0135] Synthesis of (5c) using 3-methylbenzyl bromide (1c) and diphenylphosphine (2a) as raw materials:

[0136]

[0137] 0.33 mmol of 3-methylbenzyl bromide (1c) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5c. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 82%.

[0138] 1 H NMR (300MHz, Chloroform-d) δ7.90–7.72(m,4H),7.58–7.36(m,6H),7.04(p,J=7.5Hz,2H),6.87–6.67(m,2H),3.82(d,J=13.5Hz,2H),2.21(s,3H). 13 C NMR(75MHz,Chloroform-d)δ137.37(d,J=3.2Hz),132.69,131.65,131.50(d,J=3.1Hz),131.34(d,J=5.3Hz),130.56(d,J=7 .5Hz), 128.40 (d, J = 12.0Hz), 127.78 (dd, J = 5.1, 3.5Hz), 127.47 (d, J = 5.3Hz), 82.35–70.06 (m), 40.82 (d, J = 50.6Hz), 21.29. 31 P NMR(121MHz,Chloroform-d)δ42.16.

[0139] Example 23

[0140] Compound (5d) was synthesized from 4-methylbenzyl bromide (1d) and diphenylphosphine (2a):

[0141]

[0142] 0.33mmol 4-methylbenzyl bromide (1d) and 0.3mmol diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0eq of S8 was added to the flask and reacted for 5 hours to obtain 5d. After the reaction was completed, 1mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 72%.

[0143] 1 H NMR(300MHz,Chloroform-d)δ7.88–7.74(m,4H),7.54–7.39(m,6H),6.98(d,J=8. 0Hz, 2H), 6.90 (dd, J=8.1, 2.3Hz, 2H), 3.83 (d, J=13.3Hz, 2H), 2.77–1.46 (m, 3H). 13 CNMR(75MHz,Chloroform-d)δ136.73(d,J=3.9Hz),132.78,131.69(d,J=4.5Hz),131.52(d,J=2.6Hz),130.3 5(d,J=5.3Hz), 128.72(d,J=3.2Hz), 128.47(d,J=12.0Hz), 127.54(d,J=7.6Hz), 40.37(d,J=50.8Hz), 21.16. 31 P NMR(121MHz,Chloroform-d)δ42.11.

[0144] Example 24

[0145] Compound (5e) was synthesized from 2-fluorobenzyl bromide (1e) and diphenylphosphine (2a):

[0146]

[0147] 0.33 mmol of 2-fluorobenzyl bromide (1e) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5e. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 75%.

[0148] 1H NMR(300MHz,Chloroform-d)δ7.89–7.75(m,4H),7.56–7.31(m,7H),7.17(tdd,J=7. 4,5.8,2.0Hz,1H),7.02(t,J=7.5Hz,1H),6.91–6.82(m,1H),3.92(d,J=13.6Hz,2H). 13 CNMR(75MHz,Chloroform-d)δ160.79(dd,J=246.5,6.2Hz),132.59,132.42(dd,J=4.5,3.5Hz),131.74–131.59(m),131.50(d,J=2.7Hz),129.0 5(dd,J=8.2,3.6Hz), 128.51(d,J=12.1Hz), 123.70(t,J=3.4Hz), 118.44(dd,J=14.8,7.3Hz), 115.05(dd,J=22.3,2.9Hz), 33.56(d,J=52.1Hz). 31 P NMR(121MHz,Chloroform-d)δ42.01. 19 F NMR (282MHz, Chloroform-d) δ-116.28 (dddd, J=10.1, 8.1, 5.4, 3.2Hz).

[0149] Example 25

[0150] Synthesis of (5f) using 3-fluorobenzyl bromide (1f) and diphenylphosphine (2a) as raw materials:

[0151]

[0152] 0.33mmol 3-fluorobenzyl bromide (1f) and 0.3mmol diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0eq of S8 was added to the flask and reacted for 5 hours to obtain 5f. After the reaction was completed, 1mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to give a white solid in a yield of 89%.

[0153] 1H NMR(300MHz,Chloroform-d)δ7.85–7.74(m,4H),7.55–7.40(m,6H),7.11(q,J=7.8Hz,1H) ,6.88(t,J=8.4Hz,1H),6.78(d,J=7.6Hz,1H),6.74–6.70(m,1H),3.83(d,J=13.6Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ162.18(dd,J=245.5,3.6Hz),133.25(t,J=7.7Hz),132.40,131.76(d,J=3.0Hz),131.66–131.25(m),12 9.29(dd,J=8.3,3.2Hz), 128.61(d,J=12.1Hz), 126.30(dd,J=5.4,2.9Hz), 117.38(dd,J=22.1,5.2Hz), 114.10(dd,J=21.0,3.6Hz). 31 PNMR(121MHz,Chloroform-d)δ41.95(d,J=5.3Hz). 19 F NMR (282MHz, Chloroform-d) δ-113.32 (tdd, J=8.8, 6.1, 2.6Hz).

[0154] Example 26

[0155] Synthesized from 4-fluorobenzyl bromide (1g) and diphenylphosphine (2a) (5g):

[0156]

[0157] 0.33 mmol of 4-fluorobenzyl bromide (1 g) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5 g. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid with a yield of 88%.

[0158] 1H NMR (300MHz, Chloroform-d) δ7.84–7.74(m,4H),7.54–7.39(m,6H),6.96(ddd,J=8.1,5.3,2.5Hz,2H),6.84(t,J=8.6Hz,2H),3.81(d,J=13.2Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ162.12(dd,J=245.8,4.0Hz),132.45,131.95(dd,J=8.0,5.2Hz),131.69(d,J=3.0Hz),131. 61,131.48,131.38,128.58(d,J=12.0Hz), 126.45(dd,J=7.5,3.2Hz), 114.88(dd,J=21.4,3.2Hz), 39.90(d,J=50.9Hz). 31 P NMR (121MHz, Chloroform-d) δ42.17 (d, J=6.1Hz). 19 F NMR (282MHz, Chloroform-d) δ-115.31 (tq, J=8.8, 5.6Hz).

[0159] Example 27

[0160] Synthesized from 2,3,4-trifluorobenzyl bromide (1q) and diphenylphosphine (2a) (5h):

[0161]

[0162] 0.33mmol 2,3,4-trifluorobenzyl bromide (1q) and 0.3mmol diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0eq of S8 was added to the flask and reacted for 5 hours to obtain 5h. After the reaction was completed, 1mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 74%.

[0163] 1 H NMR (300MHz, Chloroform-d) δ7.86–7.77(m,4H),7.48(dddd,J=14.3,9.9,6.2,2.6Hz,6H),7.16–7.04(m,1H),6.91–6.79(m,1H),3.87(d,J=13.2Hz,2H). 13C NMR(75MHz,Chloroform-d)δ156.05–147.48(m),143.55–136.74(m),132.17,132.00(d,J=3.0Hz),131.47(d,J=10.1Hz),131 .10,128.72(d,J=12.2Hz),125.74(dd,J=8.1,3.8Hz),117.70–114.82(m),111.66(dt,J=17.3,3.5Hz),33.17(d,J=52.0Hz). 31 P NMR (121MHz, Chloroform-d) δ41.75 (dt, J=5.8, 2.8Hz). 19 F NMR(282MHz,Chloroform-d)δ-135.27(ddq,J=22.6,13.1,6.2Hz),-135.76–-136.49(m),-160.42(tdt,J=20.7,7.4,2.6Hz).

[0164] Example 28

[0165] Compound (5i) was synthesized from 2-chloro-4-ethoxy-6-fluorobenzyl bromide (1p) and diphenylphosphine (2a):

[0166]

[0167] 0.33 mmol of 2-chloro-4-ethoxy-6-fluorobenzyl bromide (1p) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5i. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 60%.

[0168] 1 H NMR (300MHz, Chloroform-d) δ7.98–7.80(m,4H),7.58–7.39(m,6H),6.33(d,J=9.4Hz,2H),4.12–3.84(m,4H),1.37(t,J=7.0Hz,3H). 13C NMR(75MHz,Chloroform-d)δ163.59(dd,J=11.0,5.1Hz),161.38–159.17(m),132.99,131.93,131.78–131.49(m) ,128.48(d,J=12.1Hz),99.94(td,J=20.4,7.6Hz),98.24(dt,J=27.1,2.6Hz),64.18,29.52(d,J=53.0Hz),14.63. 31 P NMR(121MHz,Chloroform-d)δ40.85. 19 F NMR (282MHz, Chloroform-d) δ-110.12 (d, J = 10.3Hz).

[0169] Example 29

[0170] Synthesis (5j) from 2-bromomethylnaphthalene (1r) and diphenylphosphine (2a):

[0171]

[0172] 0.33 mmol of 2-bromomethylnaphthalene (1r) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a N2 atmosphere at 30°C until the starting material completely disappeared (10 hours). After the reaction, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5j. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 52%.

[0173] 1 H NMR (300MHz, Chloroform-d) δ7.86–7.74(m,5H),7.64(d,J=8.8Hz,2H),7.55–7.39(m,9H),7.13(d,J=8.5Hz,1H),4.00(d,J=13.5Hz,2H). 13C NMR(75MHz,Chloroform-d)δ133.07(d,J=3.3Hz),132.75,132.44(d,J=2.7Hz),131.94–131.56(m),129.58(d,J=7.0Hz),12 8.69–128.46(m),128.37,127.70(dd,J=7.6,1.6Hz),127.47(d,J=2.6Hz),125.92(dd,J=12.8,1.4Hz),41.19(d,J=50.5Hz). 31 P NMR(121MHz,Chloroform-d)δ42.07.

[0174] Example 30

[0175] Synthesis (5k) from 4-bromomethyl-1,1-difluorocyclohexane (1s) and diphenylphosphine (2a):

[0176]

[0177] 0.33 mmol of 4-bromomethyl-1,1-difluorocyclohexane (1s) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at 100°C until the starting material completely disappeared (72 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5k. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid with a yield of 65%.

[0178] 1 H NMR(300MHz,Chloroform-d)δ7.85(ddd,J=12.8,7.7,1.8Hz,4H),7.52–7.41(m,6H),2.45(dd,J= 11.6, 6.3Hz, 2H), 2.15 (s, 1H), 1.93 (td, J = 7.0, 3.7Hz, 2H), 1.77–1.53 (m, 4H), 1.36–1.23 (m, 2H). 13C NMR(75MHz,Chloroform-d)δ133.43(d,J=79.8Hz),131.58(d,J=2.9Hz),130.94(d,J=10.1Hz),128.75(d,J =12.0Hz), 37.56 (dd, J = 55.8, 2.6Hz), 33.31 (d, J = 2.0Hz), 33.31 (d, J = 48.2Hz), 31.24, 30.35 (t, J = 9.2Hz). 31 P NMR(121MHz,Chloroform-d)δ40.18. 19 FNMR(282MHz,Chloroform-d)δ-91.98(d,J=235.3Hz),-102.22(d,J=235.1Hz).

[0179] Example 31

[0180] Synthesis (5l) from (E)-(3-bromopropyl-1-enyl)benzene (1t) and diphenylphosphine (2a):

[0181]

[0182] 0.33 mmol (E)-(3-bromopropyl-1-enyl)benzene (1t) and 0.3 mmol diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at 30°C until the starting material completely disappeared (12 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5l. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid with a yield of 70%.

[0183] 1 H NMR(300MHz,Chloroform-d)δ7.85(ddd,J=12.8,7.9,1.6Hz,4H),7.50(td,J=7.8,2.3Hz,6H),7.33 –7.17(m,5H),6.39(dd,J=15.8,5.0Hz,1H),6.31–6.12(m,1H),3.47(ddd,J=14.5,7.3,1.1Hz,2H). 13C NMR(75MHz,Chloroform-d)δ136.80(d,J=3.6Hz),135.86(d,J=13.4Hz),133.00,131.94,131.72(d,J=3.0Hz),131.48(d,J= 9.9Hz), 128.81, 128.62 (d, J = 3.9Hz), 127.76 (d, J = 1.3Hz), 126.43 (d, J = 2.0Hz), 118.88 (d, J = 9.2Hz), 38.88 (d, J = 53.9Hz). 31 PNMR(121MHz,Chloroform-d)δ40.75.

[0184] Example 32

[0185] Synthesis (5m) from (2-bromoethyl)cyclopropane (1u) and diphenylphosphine (2a):

[0186]

[0187] 0.33 mmol (2-bromoethyl)cyclopropane (1u) and 0.3 mmol diphenylphosphine (2a) were added to a reaction flask and reacted at 100°C under a N2 atmosphere until the starting material completely disappeared (12 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5m. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid with a yield of 55%.

[0188] 1 H NMR(300MHz,Chloroform-d)δ7.83(ddd,J=12.8,7.8,1.7Hz,4H),7.45(dd,J=7.4,2.6Hz,6H),2. 67–2.48(m,2H),1.59–1.46(m,2H),0.81–0.66(m,1H),0.48–0.35(m,2H),0.03(q,J=4.9Hz,2H). 13 C NMR(75MHz,Chloroform-d)δ133.01(d,J=79.7Hz),131.49(d,J=2.9Hz),131.13(d,J=1 0.1Hz), 128.70 (d, J = 11.9Hz), 32.65 (d, J = 55.9Hz), 27.52, 11.89 (d, J = 19.8Hz), 4.90. 31P NMR(121MHz,Chloroform-d)δ42.12.

[0189] Example 33

[0190] Synthesis (5n) from 2-iodoethylbenzene (7a) and diphenylphosphine (2a):

[0191]

[0192] 0.33mmol 2-iodoethylbenzene (7a) and 0.3mmol diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw material completely disappeared (10 hours). After the reaction was completed, 3.0eq of S8 was added to the flask and reacted for 5 hours to obtain 5n. After the reaction was completed, 1mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 93%.

[0193] 1 H NMR(300MHz,Chloroform-d)δ7.89–7.80(m,4H),7.45(dd,J=7.8,2.4Hz,6H),7.27–7.12(m,5H),2.97–2.87(m,2H),2.79–2.68(m,2H). 13 C NMR(75MHz,Chloroform-d)δ140.82(d,J=17.0Hz),133.01,131.95,131.56(d,J=2.9Hz),131.04(d,J= 10.1Hz), 128.61 (d, J = 1.3Hz), 128.49 (d, J = 42.7Hz), 126.36, 34.50 (d, J = 54.7Hz), 28.33 (d, J = 1.4Hz). 31 P NMR(121MHz,Chloroform-d)δ41.98.

[0194] Example 34

[0195] Synthesis of (5o) using 2-iodopropylbenzene (7b) and diphenylphosphine (2a) as raw materials:

[0196]

[0197] 0.33 mmol of 2-iodopropylbenzene (7b) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5o. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid with a yield of 98%.

[0198] 1 H NMR(300MHz,Chloroform-d)δ7.75(ddd,J=12.8,7.8,1.4Hz,4H),7.41(pd,J=8.7,8.2,4.1Hz,6H),7.20(d d,J=16.6,7.2Hz,3H),7.09(d,J=6.9Hz,2H),2.69(t,J=7.4Hz,2H),2.53–2.33(m,2H),2.08–1.90(m,2H). 13 C NMR (75MHz, Chloroform-d) δ140.75, 133.20, 132.14, 131.42 (d, J = 2.9 Hz), 131.00 (d, J = 10. 1Hz),128.68,128.56–128.38(m),126.11,36.27(d,J=16.7Hz),31.64(d,J=56.9Hz),23.73. 31 P NMR(121MHz,Chloroform-d)δ42.68.

[0199] Example 35

[0200] Synthesis (5p) from benzyl bromide (1a) and diisopropylphosphine (2b):

[0201]

[0202] 0.33 mmol of benzyl bromide (1a) and 0.3 mmol of diisopropylphosphine (2b) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5p. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 70%.

[0203] 1H NMR (300MHz, Chloroform-d) δ7.40(d,J=7.7Hz,2H),7.36–7.24(m,3H),3.28(d,J=12.8Hz,2H),2.52–2.02(m,2H),1.18(ddd,J=16.7,7.0,4.2Hz,12H). 13 C NMR(75MHz,Chloroform-d)δ132.34(d,J=7.4Hz),129.98(d,J=4.8Hz),128.45(d,J=2.4Hz),127.16( d,J=2.9Hz), 84.29–70.46(m), 35.22(d,J=42.2Hz), 27.40(d,J=47.8Hz), 16.48(dd,J=23.6,2.3Hz). 31 P NMR(121MHz,Chloroform-d)δ65.38.

[0204] Example 36

[0205] Synthesis (5q) from benzyl bromide (1a) and di-tert-butylphosphine (2c):

[0206]

[0207] 0.33 mmol of benzyl bromide (1a) and 0.3 mmol of di-tert-butylphosphine (2c) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5q. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to obtain a white solid with a yield of 81%.

[0208] 1 H NMR (300MHz, Chloroform-d) δ7.56(d,J=7.8Hz,2H),7.35–7.19(m,3H),3.33(d,J=11.5Hz,2H),1.30(d,J=14.7Hz,18H). 13 C NMR(75MHz,Chloroform-d)δ133.58(d,J=7.1Hz),130.68(d,J=4.7Hz),128.04(d,J=2.0Hz ),126.91(d,J=2.6Hz),80.65–73.84(m),38.47(d,J=40.0Hz),31.29(d,J=37.7Hz),27.92.31 P NMR(121MHz,Chloroform-d)δ76.92.

[0209] Example 37

[0210] Compound (5r) was synthesized from benzyl bromide (1a) and dicyclohexylphosphine (2d):

[0211]

[0212] 0.33 mmol of benzyl bromide (1a) and 0.3 mmol of dicyclohexylphosphine (2d) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5r. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, and the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 81%.

[0213] 1 H NMR (300MHz, Chloroform-d) δ7.78–7.21(m,5H),3.26(d,J=12.8Hz,2H),2.26–1.63(m,12H),1.57–1.11(m,10H). 13 C NMR(75MHz,Chloroform-d)δ132.49(d,J=7.3Hz),130.00(d,J=4.8Hz),128.38(d,J=2.4Hz),127.10(d,J=2.9Hz),3 7.24(d,J=46.9Hz), 35.24(d,J=42.3Hz), 26.57(dd,J=12.8,6.1Hz), 26.09(dd,J=13.0,3.0Hz), 25.82(d,J=1.5Hz). 31 P NMR(121MHz,Chloroform-d)δ58.01.

[0214] Example 38

[0215] Synthesized from benzyl bromide (1a) and di-p-methylphenylphosphine (2e) (5s):

[0216]

[0217] 0.33 mmol of benzyl bromide (1a) and 0.3 mmol of di-p-methylphenylphosphine (2e) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of S8 was added to the flask and reacted for 5 hours to obtain 5s. After the reaction was completed, 1 mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 37%.

[0218] 1 H NMR(300MHz,Chloroform-d)δ7.66(dd,J=12.5,8.1Hz,4H),7.20(ddd,J=21.4,8 .9,3.2Hz,7H),7.00(dt,J=7.6,2.3Hz,2H),3.81(d,J=13.6Hz,2H),2.39(s,6H). 13 C NMR (75MHz, Chloroform-d) δ142.05 (d, J = 3.0Hz), 131.70 (d, J = 10.2Hz), 131.19 (d, J = 7.5Hz), 130.60 (d, J = 5.3Hz), 129.30(d,J=12.5Hz), 129.12(d,J=82.6Hz), 128.02(d,J=3.2Hz), 127.13(d,J=3.7Hz), 41.19(d,J=50.9Hz), 21.62. 31 P NMR(121MHz,Chloroform-d)δ41.62.

[0219] Example 39

[0220] Synthesis (5t) from benzyl bromide (1a) and di(2-methoxy)phenylphosphine (2f):

[0221]

[0222] 0.33mmol of benzyl bromide (1a) and 0.3mmol of di(2-methoxy)phenylphosphine (2f) were added to a reaction flask and reacted under N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0eq of S8 was added to the flask and reacted for 5 hours to obtain 5t. After the reaction was completed, 1mL of ammonium chloride solution was added to quench S8, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and chromatographed with n-hexane:ethyl acetate = 10:1 to obtain a white solid in a yield of 50%.

[0223] 1H NMR(300MHz,Chloroform-d)δ7.58(ddd,J=15.5,7.8,1.6Hz,2H),7.43(t,J=7.8Hz, 2H),7.07(s,5H),6.92(dt,J=8.3,5.7Hz,4H),4.22(d,J=15.9Hz,2H),3.77(s,6H). 13 C NMR(75MHz,Chloroform-d)δ159.88(d,J=2.6Hz),134.52(d,J=8.9Hz),133.19(d,J=2.4Hz),132.45(d,J=7.9Hz),130.21(d,J=6.0Hz),1 27.64(d,J=3.5Hz), 126.67(d,J=4.1Hz), 120.93(d,J=12.4Hz), 120.71(d,J=82.5Hz), 111.18(d,J=6.3Hz), 55.65, 39.60(d,J=52.2Hz). 31 P NMR(121MHz,Chloroform-d)δ42.17.

[0224] Example 40

[0225] Synthesis of (6a) using 2-iodoethylbenzene (7a) and diphenylphosphine (2a) as raw materials:

[0226]

[0227] 0.33 mmol of 2-iodoethylbenzene (7a) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a N2 atmosphere at room temperature until the raw materials completely disappeared (10 hours). After the reaction was completed, 3.0 eq of borane dimethyl sulfide complex was added to the flask and reacted at room temperature for 4 hours to obtain 6a. After the reaction was completed, 3 mL of ammonium chloride solution was added to quench the borane dimethyl sulfide complex, and then a large amount of water was added. The product was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 20:1 to obtain a white solid in a yield of 98%.

[0228] 1 H NMR(300MHz,Chloroform-d)δ7.68(ddd,J=10.4,7.8,1.5Hz,4H),7.53–7.33(m, 6H),7.28–7.10(m,5H),2.86–2.74(m,2H),2.57–2.43(m,2H),1.70–0.65(m,3H). 13C NMR (75MHz, Chloroform-d) δ 141.22 (d, J = 14.9 Hz), 132.15 (d, J = 9.1 Hz), 131.33 (d, J = 2.4 Hz), 129. 16(d,J=55.0Hz), 128.94(d,J=9.9Hz), 128.37(d,J=43.1Hz), 126.43, 29.18, 27.81(d,J=35.5Hz). 31 P NMR (121MHz, Chloroform-d) δ15.66 (d, J=68.3Hz).

[0229] Example 41

[0230] Synthesis of (6b) using 2-iodopropylbenzene (7b) and diphenylphosphine (2a) as raw materials:

[0231]

[0232] 0.33 mmol of 2-iodopropylbenzene (7b) and 0.3 mmol of diphenylphosphine (2a) were added to a reaction flask and reacted under a N2 atmosphere at room temperature until the starting material completely disappeared (10 hours). After the reaction was completed, 3.0 eq of borane dimethyl sulfide complex was added to the flask and reacted at room temperature for 4 hours to obtain 6b. After the reaction was completed, 3 mL of ammonium chloride solution was added to quench the borane dimethyl sulfide complex, and then a large amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phases were combined, concentrated in vacuo, and purified by column chromatography using n-hexane:ethyl acetate = 20:1 to obtain a white solid in a yield of 84%.

[0233] 1 H NMR(300MHz,Chloroform-d)δ7.66–7.51(m,4H),7.48–7.28(m,6H),7.18(dt,J=16.6,7.4Hz,3H),7. 08(d,J=7.1Hz,2H),2.66(t,J=7.3Hz,2H),2.23–2.09(m,2H),1.91–1.77(m,2H),1.45–0.54(m,3H). 13 C NMR(75MHz,Chloroform-d)δ140.80,132.13(d,J=9.0Hz),131.20(d,J=2.4Hz),129.77,129.04,1 28.85(d,J=9.8Hz),128.52(d,J=3.5Hz),126.18,36.85(d,J=14.2Hz),25.10,24.57(d,J=4.4Hz). 31P NMR(121MHz,Chloroform-d)δ15.86(d,J=70.4Hz).

Claims

1. A method for synthesizing a trisubstituted phosphine and its oxygen / sulfur / boride, characterized in that: The synthesis method comprises the following steps: mixing a raw material halide and a diaryl / alkyl phosphine, reacting the mixture under an inert gas atmosphere until the raw material disappears, and then further oxidizing / sulfurizing / boranizing the mixture, followed by separation and purification to obtain a trisubstituted phosphine oxide / sulfur / boride. The reaction formula of the synthesis method is shown in Formula I below: In formula I, X is Br or I; R 1 is selected from benzene and its substituents, naphthyl, 3-8 C cycloalkyl and its substituents; said R 1 The substituents of the benzene substituent are selected from 1-8 C alkyl, 1-8 C alkenyl, halogen, 1-8 C haloalkyl, 1-8 C alkoxy, 1-8 C haloalkoxy, the number is 1-4, and the position is any position of the benzene ring; the R 1 The substituent of the cycloalkyl substituent is selected from 1-8 C alkyl, 1-8 C alkenyl, and halogen; R 2 is selected from benzene and its substituents, 1-8 C alkyl, 3-8 C cycloalkyl; said R 2 The substituents of the benzene substituent are selected from 1-8 C alkyl and 3-8 C alkoxy, the number is 1-4, and the position is any position of the benzene ring.

2. The method for synthesizing a trisubstituted phosphine and its oxygen / sulfur / boride according to claim 1, characterized in that: The molar ratio of the halide to the diaryl / alkyl phosphine compound is 1-1.1:

1.

3. The synthesis method according to claim 1, wherein The reaction temperature is room temperature to 100°C.

4. The synthesis method according to claim 1, characterized in that The R 1 One selected from phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-trifluoromethylphenyl, p-trifluoromethoxyphenyl, 3,4-difluorophenyl, 2,6-dichlorophenyl, 2-fluoro-6-chlorophenyl, 2-fluoro-4-ethoxy-6-chlorophenyl, 2,3,4-trifluorophenyl, naphthyl, 4,4-difluorocyclohexyl, styryl, cyclopropylmethyl, benzyl, and phenethyl.

5. The synthesis method according to claim 1, characterized in that The R 2 One selected from phenyl, p-methylphenyl, 2-methoxyphenyl, isopropyl, tert-butyl and cyclohexyl.

6. The synthesis method according to claim 1, characterized in that The oxidation method is contact with oxygen.

7. The synthesis method according to claim 1, characterized in that The sulfurization method is to react with S8.

8. The synthesis method according to claim 1, characterized in that The boranylation method is a BH3·SMe2 reaction.

9. The synthesis method according to claim 1, characterized in that The reaction time is 10 to 72 hours.

10. The trisubstituted phosphine and oxygen / sulfur / boride thereof according to claim 1, specifically comprising the following compounds:

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