Phosphabicyclo[3,2,0] organophosphorus compounds, methods of making and using the same

Abstract

The application discloses a phosphorus heterocyclic [3,2,0] organic phosphorus compound and a preparation method and application thereof. A phosphorus heterocyclic [3,2,0] organic phosphorus compound containing two quaternary carbon centers is synthesized by using a phosphine oxygen compound containing a double allyl group and a phosphine sulfur compound as raw materials, using 10-phenyl phenothiazine as a photocatalyst, exciting the photocatalyst under a 390 nm light source to activate the double bond, realizing a high stereoselectivity [2+2] cycloaddition reaction, and separating diastereoisomers, wherein a single diastereoisomer product is as high as 97%, and the diastereoselectivity is excellent. The application provides a green reaction mode for synthesizing the phosphorus heterocyclic [3,2,0] organic phosphorus compound by photocatalysis, and the reaction condition is mild, and the substrate universality is good. The obtained phosphorus heterocyclic [3,2,0] organic phosphorus compound is applied to primary alcohol chlorination as a catalyst, and exhibits high reactivity, and compared with a reported catalytic system, the application has more excellent catalytic activity.

Description

Technical Field

[0001] This invention belongs to the field of compound and catalytic technology, and relates to a method for preparing a phosphorus heterobicyclic [3,2,0] organophosphorus compound and its application, and more specifically to the above-mentioned organophosphorus compound as a catalyst for the reaction of primary alcohol to chlorinated hydrocarbon. Background Technology

[0002] In organic synthesis methodology, the resurgence of radical chemistry has led researchers to focus on photocatalysis. Driven by light energy, photocatalysts interact with substrates via electron transfer, generating highly reactive radical intermediates that trigger a series of unique reaction pathways. Photocatalytic [2+2] cycloaddition reactions provide an efficient route to obtain multi-carbon ring or heterocyclic organic compounds [Chem. Rev., 2016, 116(17), 9748-9815.], but no reports have been found on phosphorus heterocyclic organophosphorus compounds. Currently, the main method for constructing phosphorus heterocyclic organophosphorus compounds involves reacting pre-prepared phosphorus-containing substrates with reactive metal reagents. This method suffers from drawbacks such as harsh reaction conditions, poor atom economy, poor functional group tolerance, numerous side reactions, low yields, or difficulty in large-scale preparation [J. Org. Chem. 2015,80, 9774–9780.]. In contrast, photocatalysis can be performed at room temperature, under mild conditions, in line with the principles of green chemistry, and can achieve highly selective cyclization reactions in a short time. Photocatalytic synthesis represents a more modern, green, and powerful synthetic strategy, providing a new route for the synthesis of phosphorus heterocyclic organophosphorus compounds.

[0003] Organophosphorus compounds are commonly used reagents in organic synthesis. The catalytic application of phosphorus reagents can be categorized into two strategies: (1) maintaining the oxidation state during the catalytic cycle (i.e., activation strategy); and (2) in-situ reduction of organophosphorus compounds, commonly seen in Witting, Mitsunobu, Staudinger, and Appel reactions. Although reported phosphorus reagent-mediated reactions exhibit good catalytic effects, the synthesis of the target product is accompanied by the generation of stoichiometric organophosphorus compound byproducts, resulting in poor atom economy and severely hindered product separation and purification. While there are reports of bypassing phosphine oxide reduction by forming a chlorophosphine salt intermediate with oxalyl chloride and organophosphorus compounds, maintaining the oxidation state of phosphine, this releases toxic carbon monoxide and hydrogen chloride gases, and the use of highly reactive oxalyl chloride requires consideration of functional group tolerance [J. Org. Chem. 2011, 76, 6749–6767]. Therefore, the P(III) / P(V) redox catalytic cycle strategy has been rapidly developed. However, the P=O bonds formed by the byproducts possess extremely high bond energies and thermodynamic stability. Therefore, finding P(V) compounds with lower reduction barriers to achieve more efficient P(III) / P(V) redox catalytic cycles is crucial for developing highly efficient catalytic systems. Cyclic P(V)=O compounds have the potential to possess lower reduction barriers compared to acyclic P(V)=O compounds [Hérault, D., Chem. Soc. Rev. 2015, 44, 2508.], but this mechanism has not yet been fully realized in the catalytic Appel reaction for the preparation of chlorinated hydrocarbons from primary alcohols. Furthermore, in the nucleophilic substitution reactions of alcohols by halides, the chlorination reaction requires more nucleophilic catalysts than the bromination reaction due to the denser electron cloud of chloride ions, making polarization difficult. These catalysts need to activate the less electrophilic halogen donors to form highly reactive phosphonium salt intermediates. Currently, it has been reported that highly catalytically active organophosphorus catalysts use tri-n-octylphosphine compounds as trivalent phosphine catalysts, which require a high catalyst equivalent (at least 10 mol%) to obtain good catalytic product yields. Summary of the Invention

[0004] This invention enables the [2+2] cycloaddition reaction to be completed within two hours under specific light source irradiation conditions using a low-load photocatalyst, constructing a phosphorus-heterobicyclic [3,2,0] organophosphorus compound containing two quaternary carbon chiral centers. This compound exhibits high chemoselectivity and excellent diastereoselectivity, is produced under mild conditions, is environmentally friendly, and has high atom economy. Furthermore, this reaction mode is applicable to various substrate framework structures. The prepared phosphorus-heterobicyclic [3,2,0] organophosphorus compound was used as a catalyst in the chlorination reaction of primary alcohols, demonstrating excellent catalytic performance.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] A phosphabicyclic [3,2,0] organophosphorus compound, wherein the general structural formula of the phosphabicyclic [3,2,0] organophosphorus compound is shown in any of the following:

[0007] ,

[0008] Where X is an oxygen atom or a sulfur atom;

[0009] Ar 1 It is a benzene ring, benzodioxane, or naphthalene ring; n is 0, 1, or 2;

[0010] R 1 It is hydrogen, trifluoromethyl, C1-C6 alkoxy or C1-C6 saturated alkyl;

[0011] R 2 It is a C1-C6 saturated alkyl, naphthyl, phenyl, or substituted phenyl; a substituted phenyl is one in which the hydrogen atom on the phenyl group can be replaced by a halogen atom or a C1-C6 saturated alkyl group.

[0012] Preferably, Ar 1 It is an aromatic ring, benzodioxane, or naphthalene ring; n is 0, 1, or 2;

[0013] R 1 It is hydrogen, trifluoromethyl, C1-C3 alkoxy or C1-C3 saturated alkyl;

[0014] R 2 It is a C1-C3 saturated alkyl, naphthyl, phenyl, or substituted phenyl; a substituted phenyl is one in which the hydrogen atom on the phenyl group can be replaced by a halogen atom or a C1-C3 saturated alkyl group; the halogen atom is chlorine or bromine.

[0015] The present invention also provides a method for preparing the above-mentioned compound, comprising the following steps:

[0016] Step S1:

[0017]

[0018] Step S1: Under inert gas protection, compound I is added to acetonitrile with a silanizing agent to obtain compound I-1. The reaction is then carried out at a specific temperature until completion, and then concentrated under reduced pressure to a dry state before being added to the next reaction step.

[0019] Step S2:

[0020]

[0021] Step S2: Under inert gas protection, compound I-1 is used as the raw material, dichloromethane is added as the solvent, and the mixture is cooled to 0°C. Under the catalysis of N,N-dimethylformamide, it is phosphonic chlorinated with an acyl chloride reagent. After the reaction is completed at room temperature, the mixture is concentrated under reduced pressure to a dry state before being added to the next reaction step.

[0022] Step S3:

[0023]

[0024] Step S3: Under inert gas protection, the dried phosphonyl chloride compound I-2 or phosphorus oxychloride was added to the dilute ether system. Freshly prepared Grignard reagent I-3 was added to the phosphonyl chloride compound I-2 or phosphorus oxychloride at 0°C, and then stirred overnight at room temperature. After extraction, the product was separated and purified by column chromatography to obtain dielyl organophosphorus compound II or II'.

[0025] Step S4:

[0026]

[0027] Step S4: Under inert gas protection, the solvent is added to the reaction system containing dielyl organophosphorus compound II and Lawson's reagent, heated to reflux until the reaction is complete, concentrated under reduced pressure, and purified to obtain compound II-S1.

[0028] Step S5:

[0029]

[0030] Step S5: Under inert gas protection, an organic solvent is added to a reaction system containing dielyl organophosphorus compound II or II-S1 or II' and a photocatalyst. The system is irradiated with a light source of a specific wavelength and reacted at room temperature. Subsequently, the mixture is concentrated under reduced pressure. The resulting concentrated crude product is purified by column chromatography to obtain the target compound III or III'.

[0031] In this invention, the photocatalyst (photosensitizer) in step S5 is selected from one of 10-phenylphenthiazine, 9,10-dicyanoanthracene, 10-methyl-9-trimethylylacrylidine perchlorate, 4,4'-bis(trifluoromethyl)-2,2'-bipyridinebis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl)phenyl]iridium hexafluorophosphate (III), tri(2-phenylpyridine)iridium, 9-trimethylyl-2,7-dimethoxy-10-phenylacrylidine tetrafluoroborate, and 3,6-di-tert-butyl-9-trimethylyl-10-phenylacrylidine-10-onium tetrafluoroborate.

[0032] In this invention, the organic solvent in step S5 can be one of dichloromethane, dichloroethane, acetonitrile, propionitrile, butyronitrile, valerate, benzonitrile, phenylacetonitrile, diethyl ether, anisole, ethyl acetate, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, benzene, chlorobenzene, fluorobenzene, trifluorotoluene, chloroform, acetone, or any mixture thereof.

[0033] In this invention, the feeding ratio of the method described in step S5 is as follows: the molar ratio between diallyl organophosphorus compound II, II-S1 or II' and photocatalyst is 1:(0.01-0.1); the molar amount of diallyl organophosphorus compound II, II-S1 or II' and the volume ratio of organic solvent is 1 mmol:(1-15) mL.

[0034] As a preferred embodiment, in the method for preparing and applying a phosphorus heterocyclic organophosphorus compound of the present invention:

[0035] In this invention, the molar ratio of the material of formula I and trimethylbromosilane in step S1 is 1:4, the reaction temperature is 50°C, and the reaction time is 2 hours.

[0036] In this invention, the molar ratio of the material of formula I-1, N,N-dimethylformamide, and acyl chloride reagent in step S2 is 1:0.05:3, the reaction temperature is room temperature, and the reaction time is 4 hours.

[0037] In this invention, the molar ratio of material formula I-2 and Grignard reagent I-3 in step S3 is 1:1.4, the reaction temperature is room temperature, the reaction time is 12 hours, and after acid-base extraction, the mixture is concentrated under reduced pressure and then post-processed by column chromatography. The molar ratio of material formula phosphorus oxychloride and Grignard reagent I-3 in step S3 is 1:1.4, the reaction temperature is room temperature, the reaction time is 12 hours, and after acid-base extraction, the mixture is concentrated under reduced pressure and then post-processed by column chromatography.

[0038] In this invention, the molar ratio of material formula II and Lawson's reagent in step S4 is 1:0.6, the reaction temperature is 80ºC, the reaction time is 12 hours, and the product is concentrated under reduced pressure and then post-processed by column chromatography.

[0039] In this invention, the molar ratio of dielyl organophosphorus compound II, II-S1 or II' to photocatalyst in step S5 is 1:0.05, the reaction temperature is room temperature, the reaction time is 2 hours, and the product is concentrated under reduced pressure and then purified by column chromatography.

[0040] More preferably in this invention, the photocatalyst in step S5 is selected from 10-phenylphenthiazide.

[0041] More preferably in this invention, the solvent in step S5 is selected from acetonitrile.

[0042] More preferably in this invention, the light source in step S5 has a specific wavelength of 390 nanometers and a power of 40 watts.

[0043] This invention also protects the application of the aforementioned phosphorus-bicyclic organophosphorus compound in catalysis; further, it protects its application in the in-situ generation of trivalent phosphine-catalyzed Appel reaction.

[0044] Furthermore, a phosphane-bicyclic [3,2,0] organophosphorus compound was used as a catalyst to catalyze the Appel reaction; the Appel reaction resulted in the formation of compounds... As the reaction substrate, the catalyst was added, followed by the sequential addition of ultra-dry toluene, phenylsilane, and hexachloroacetone. The reaction system was sealed and reacted at 100°C for 24 hours to obtain... .

[0045] Specifically, excellent catalytic performance was achieved with a catalyst dosage of 5 mol% based on the reaction substrate. Compared to previously reported organophosphorus compounds as catalysts [J. Org. Chem. 2019, 84, 7863−7870], the phenylethanol Appel reaction requires 10 mol% of the catalyst, while the phosphorobicyclic [3,2,0] organophosphorus compound is reduced to 5 mol%, and the amount of chloride is also reduced, resulting in better yields than reported in the literature.

[0046] Regarding the definition of terms used in this invention: Unless otherwise stated, the initial definitions provided for groups or terms herein apply to the groups or terms used throughout this specification; for terms not specifically defined herein, the meanings that a person skilled in the art would give them should be given based on the disclosure and context.

[0047] "Substitution" refers to the replacement of hydrogen atoms in a molecule by other different atoms or molecules.

[0048] The minimum and maximum carbon atom content in hydrocarbon groups are indicated by prefixes. For example, the prefix (Ca~Cb)alkyl indicates any alkyl group containing "a" to "b" carbon atoms. Therefore, for example, (C1~C4)alkyl refers to an alkyl group containing 1 to 4 carbon atoms.

[0049] The C1-C6 alkyl groups refer to alkyl groups of C1, C2, C3, C4, C5, and C6, that is, straight-chain or branched alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, hexyl, etc. The alkoxy groups of C1-C6 also have the corresponding meanings of their respective groups.

[0050] Compared with the prior art, the beneficial effects of the present invention are:

[0051] This invention enables the efficient construction of a phosphorus-heterobicyclic [3,2,0] organophosphorus compound containing two quaternary carbon chiral centers through a [2+2] cycloaddition reaction with a low-load photocatalyst under specific light source irradiation conditions within two hours. This process exhibits high chemoselectivity and excellent diastereoselectivity, is conducted under mild conditions, is environmentally friendly, and boasts high atom economy. Furthermore, this reaction mode is applicable to various substrate framework structures. The resulting phosphorus-heterobicyclic organophosphorus compound is used as a catalyst in the Appel reaction to achieve the chlorination of alcohols, yielding excellent catalytic performance. Attached Figure Description

[0052] Figure 1 This is the single-crystal diffraction structure of compound III-1 of the present invention. Detailed Implementation

[0053] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods used in the embodiments of the present invention are conventional methods; the materials and reagents used, unless otherwise specified, are commercially available reagents and materials.

[0054] Example 1 Synthesis of dielyl organophosphorus compound II:

[0055] Starting with diethyl phosphite compound I, a bromosilane reagent was added to acetonitrile and reacted at 50 °C for 2 hours to obtain compound I-1. The mixture was then concentrated under reduced pressure to a dry state before being added to the next reaction step. In the second step, using N,N-dimethylformamide as a catalyst, the reaction system was diluted with dichloromethane and subjected to phosphonochlorination with oxaloyl chloride at 0 °C. The reaction was then carried out at room temperature until completion to obtain compound I-2, a phosphonochloride compound, which was concentrated under reduced pressure to a dry state. After purging the reaction system with argon gas 3–5 times using compound I-2 or phosphorus oxychloride, the reaction system was diluted with diethyl ether, and the freshly prepared Grignard reagent I-3 was added at 0 °C. The mixture was then stirred overnight at room temperature. After quenching the reaction, separation, filtration, drying, concentration under reduced pressure, and purification, dielyl organophosphorus compounds II or II' were obtained. The synthetic steps are as follows (those skilled in the art can determine each R group based on the structural formulas of compounds I-1 to I-3, and will not be elaborated further):

[0056]

[0057] Step S1: After purging with argon three times, trimethylbromosilane (40 mmol) was added to acetonitrile (10 mL) to the starting material compound I (10 mmol). The mixture was reacted at 50 °C for two hours to obtain compound I-1. The mixture was then concentrated under reduced pressure to a dry state before being added to the next reaction step.

[0058] Step S2: After purging with argon three times, at 0 °C, oxalyl chloride (30 mmol) was chlorinated with N,N-dimethylformamide (2-3 drops) as a catalyst. Compound I-1 was chlorinated with oxalyl chloride (30 mmol) in dichloromethane (10 mL). After reacting at room temperature for 4 hours, the mixture was concentrated under reduced pressure to a dry state to obtain phosphonyl chloride compound I-2.

[0059] Step S3: After purging with argon three times, compound I-2 or phosphorus oxychloride was added to diethyl ether (10 mL) at 0 °C. The freshly prepared Grignard reagent (15 mmol) was then added to the phosphonyl chloride compound I-2 or phosphorus oxychloride, and the mixture was stirred overnight at room temperature. Subsequently, a saturated ammonium chloride solution (50 mL) was added to quench the reaction. After three extractions with ethyl acetate, the organic phase was washed with a saturated sodium bicarbonate solution (50 mL) and concentrated under reduced pressure. The crude product was purified by column chromatography using petroleum ether:ethyl acetate in a 3:1 ratio to obtain the diallyl organophosphorus compound.

[0060] The characteristics of each dielyl organophosphorus compound are as follows:

[0061] The characterization data of compound II-1 are as follows:

[0062]

[0063] White solid (2.0 g, 56% yield). Melting point: 88.1–92.9 °C. 31 P{ 1 H} NMR (162 MHz, CDCl3)δ 35.60. 1 H NMR (400 MHz, CDCl3)δ 7.52 (dd, 2H), 7.37 (td, J = 7.3, 1.5Hz, 1H), 7.29 – 7.20 (m, 12H), 5.37 (d, J = 4.5 Hz, 2H), 5.17 (d, J = 4.6 Hz, 2H), 3.30 – 3.10 (m, 4H). 13 C{ 1 H} NMR (126 MHz, CDCl3)δ 141.23 (d, JC-P = 3.3 Hz), 139.00 (d, J C-P = 8.7 Hz), 131.57 (d, J C-P = 2.8 Hz), 131.44 (d, J C-P = 95.2 Hz), 131.13 (d, J C-P = 8.9 Hz), 128.45, 128.11 (d, J C-P = 11.5 Hz), 127.80, 126.45,117.94 (d, J C-P = 8.8 Hz), 37.28 (d, J C-P = 63.4 Hz).FT-IR (KBr): 3085, 3053, 2945,2905, 1621, 1573, 1493, 1437, 1303, 1231, 1192, 1115, 1092, 1070, 1029, 945,894, 869, 776, 761, 744, 727, 698, 627, 613, 589, 523, 491, 481, 470 cm -1 HRMS(ESI)calcd for C 24 H 24 OP + [M+H] + 359.1559, found 359.1561.

[0064] The characterization data of compound II-2 are as follows:

[0065]

[0066] White solid (1.3 g, 34% yield). Melting point: 128.2–133.0 °C. 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 41.97. 1 H NMR (500 MHz, CDCl3) δ 7.36 – 7.32 (m, 5H), 7.32 – 7.27 (m,5H), 7.26 – 7.20 (m, 3H), 7.13 (dt,J = 7.8, 1.8 Hz, 2H), 5.48 (d, J = 4.3 Hz, 2H), 5.30 (d, J = 4.4 Hz, 2H), 2.98 – 2.83 (m, 6H). 13 C NMR (126 MHz, CDCl3)δ141.00 (d, J C-P = 3.5 Hz), 139.22 (d, J C-P = 8.1 Hz), 131.77 (d, J C-P = 7.4 Hz), 129.96 (d, J C-P = 5.3 Hz), 128.69, 128.67, 128.09, 126.91 (d, J C-P = 2.9 Hz), 126.37, 118.00 (d, J C-P = 8.8 Hz), 35.89 (d, J C-P = 60.9 Hz), 34.92 (d, J C-P = 60.6Hz).FT-IR (KBr): 3083, 3057, 3028, 2951, 2911, 1673, 1599, 1495, 1445, 1412,1301, 1275, 1238, 1190, 1147, 1129, 1067, 1029, 913, 903, 862, 780, 733, 700,487 cm -1 HRMS (ESI)calcd for C 25 H 26 OP + [M+H] + 373.1716, found 373.1721.

[0067] The characterization data of compound II-3 are as follows:

[0068]

[0069] White solid (2.0 g, 52% yield). Melting point: 135.0–156.5 °C. 31 P{1 H} NMR (162 MHz,CDCl3)δ 33.76. 1 H NMR (400 MHz, CDCl3)δ 7.78 (ddd, J = 12.4, 7.5, 1.8 Hz, 1H),7.30 (td, J = 8.2, 1.8 Hz, 1H), 7.24 – 7.12 (m, 10H), 6.95 (tt, J = 7.5, 1.2 Hz,1H), 6.47 (dd, J = 8.3, 5.5 Hz, 1H), 5.31 (dd, J = 5.0, 1.2 Hz, 2H), 5.22 (dd, J =5.0, 1.1 Hz, 2H), 3.51 (s, 3H), 3.38 – 3.20 (m, 4H). 13 C NMR (100 MHz, CDCl3)δ158.43 (d, J C-P = 5.1 Hz), 141.39 (d, J C-P = 3.2 Hz), 139.34 (d, J C-P = 9.9 Hz),135.23 (d, J C-P = 4.3 Hz), 133.48 (d, J C-P = 2.2 Hz), 127.84, 127.16, 126.25 (d, J C-P = 1.2 Hz), 120.57 (d, J C-P = 10.5 Hz), 118.57 (d, J C-P = 93.4 Hz), 117.01 (d, J C-P =9.2 Hz), 109.39 (d, J C-P = 6.9 Hz), 54.52, 36.34 (d, J C-P= 64.1 Hz).FT-IR (KBr):3085, 3050, 2901, 2834, 1621, 1590, 1575, 1493, 1478, 1463, 1444, 1431, 1406,1302, 1274, 1242, 1223, 1199, 1155, 1078, 1023, 940, 907, 897, 855, 775, 756,732, 707, 639, 587, 501, 479, 417 cm -1 HRMS (ESI)calcd for C 25 H 26 O2P + [M+H] + 389.1665, found 389.1669.

[0070] The characterization data of compound II-4 are as follows:

[0071]

[0072] White solid (2.1 g, 50% yield). Melting point: 93.3–97.9 °C. 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 34.93. 1 H NMR (500 MHz, CDCl3)δ 7.49 (ddd, J = 11.2, 8.1, 1.3 Hz, 2H),7.40 (td, J = 7.4, 1.4 Hz, 1H), 7.28 (td, J = 7.5, 2.8 Hz, 2H), 7.22 – 7.15 (m,8H), 5.34 (d, J = 4.5 Hz, 2H), 5.13 (d, J = 4.5 Hz, 2H), 3.26 – 3.08 (m, 4H). 13 CNMR (126 MHz, CDCl3)δ 139.42 (d, J C-P = 3.2 Hz), 137.95 (d, J C-P = 9.1 Hz), 133.61,131.69 (d, J C-P= 2.8 Hz), 131.04 (d, J C-P = 95.6 Hz), 130.98 (d, J C-P = 9.0 Hz), 128.46, 128.22 (d, J C-P = 11.8 Hz), 127.77, 118.31 (d, J C-P = 8.9 Hz), 37.27 (d, J C-P = 63.4 Hz). FT-IR (KBr): 3081, 3052, 2904, 1616, 1590, 1493, 1436, 1411,1396, 1299, 1188, 1156, 1113, 1095, 1011, 943, 904, 863, 832, 765, 733, 695,676, 651, 628, 490, 473, 455, 440, 422 cm -1 HRMS (ESI)calcd for C 27 H 29 F3O2P + [M+H] + 473.1852, found 473.1854.

[0073] The characterization data of compound II-5 are as follows:

[0074]

[0075] Brown oily substance (1.3 g, 32% yield). 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 38.14. 1 HNMR (500 MHz, CDCl3)δ 8.63 (d, J = 8.4 Hz, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.79(d, J = 7.9 Hz, 1H), 7.67 (dd, J = 14.2, 7.1 Hz, 1H), 7.52 (ddd, J = 8.4, 6.7, 1.6Hz, 1H), 7.48 (t,J = 6.7 Hz, 1H), 7.29 (td, J = 7.7, 2.3 Hz, 1H), 7.21 – 7.17(m, 4H), 7.16 – 7.12 (m, 6H), 5.31 (d, J = 4.4 Hz, 2H), 5.16 (d, J = 4.6 Hz, 2H),3.51 – 3.36 (m, 4H). 13 C NMR (126 MHz, CDCl3) δ 141.07 (d, J C-P = 3.5 Hz), 139.33(d, J C-P = 8.5 Hz), 133.64 (d, J C-P = 9.3 Hz), 133.45 (d, J C-P = 8.9 Hz), 132.90 (d, J C-P = 3.1 Hz), 132.71 (d, J C-P = 8.5 Hz), 129.17, 128.82 (d, J C-P = 67.2 Hz),128.24, 127.67, 127.17, 126.40, 126.14, 126.10 (d, J C-P = 3.8 Hz), 124.27 (d, J C-P = 12.8 Hz), 118.04 (d, J C-P = 9.0 Hz), 37.56 (d, J C-P = 63.9 Hz). FT-IR (KBr):3080, 3055, 2959, 2918, 1673, 1506, 1495, 1445, 1271, 1208, 1182, 1156, 1143,1027, 985, 801, 774, 758, 730, 698, 670, 441, 432 cm -1 . HRMS (ESI)calcd forC28 H 26 OP + [M+H] + 409.1716, found 409.1722.

[0076] The characterization data of compound II-6 are as follows:

[0077]

[0078] Brown oily substance (925 mg, 23% yield). 31 P{ 1 H} NMR (162 MHz, CDCl3)δ 35.75. 1 HNMR (400 MHz, CDCl3)δ 7.29 – 7.26 (m, 5H), 7.25 – 7.20 (m, 5H), 7.05 (ddd, J =11.7, 7.9, 1.5 Hz, 1H), 6.86 (dd, J = 10.5, 1.4 Hz, 1H), 6.68 (dd, J = 7.9, 2.4Hz, 1H), 5.92 (s, 2H), 5.39 (d, J = 4.6 Hz, 2H), 5.18 (d, J = 4.6 Hz, 2H), 3.25 –3.07 (m, 4H). 13 C NMR (126 MHz, CDCl3)δ 150.41 (d, J C-P = 3.0 Hz), 147.49 (d, J C-P =17.6 Hz), 141.11 (d, J C-P = 3.4 Hz), 138.94 (d, J C-P = 8.7 Hz), 132.10 (d, J C-P = 9.7Hz), 128.33, 127.67, 126.36, 124.16 (d, J C-P = 99.0 Hz), 117.83 (d, J C-P = 9.0 Hz), 110.52 (d, JC-P = 11.9 Hz), 108.22, 101.41, 37.33 (d, J C-P = 63.9 Hz). FT-IR (KBr):3056, 3025, 2901, 1674, 1501, 1484, 1446, 1426, 1338, 1301, 1244, 1184, 1143,1114, 1064, 1036, 932, 900, 809, 777, 755, 729, 699, 641, 599, 420 cm -1 HRMS(ESI)calcd for C 25 H 24 O3P + [M+H] + 403.1458 was found; 403.1464 was also found.

[0079] The characterization data of compound II-7 are as follows:

[0080]

[0081] Colorless oil (1.3 g, 34% yield). 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 38.13. 1 HNMR (500 MHz, CDCl3)δ 7.41 (ddd, J = 12.5, 7.7, 1.4 Hz, 1H), 7.25 – 7.20 (m,11H), 7.07 (tt, J = 7.6, 1.8 Hz, 1H), 7.02 (dd, J = 7.8, 4.3 Hz, 1H), 5.34 (d, J =4.3 Hz, 2H), 5.19 (d, J = 4.4 Hz, 2H), 3.34 – 3.17 (m, 4H), 2.47 (s, 3H). 13 C NMR(126 MHz, CDCl3)δ 141.62 (d, J C-P = 8.3 Hz), 141.14 (d, J C-P = 3.6 Hz), 139.19 (d, JC-P = 8.5 Hz), 132.10 (d, J C-P = 10.1 Hz), 131.46 (d, J C-P = 10.9 Hz), 131.38 (d, J C-P = 2.7 Hz), 129.29 (d, J C-P = 91.9 Hz), 128.15, 127.51, 126.24, 125.08 (d, J C-P =11.8 Hz), 117.63 (d, J C-P = 8.8 Hz), 36.98 (d, J C-P = 63.1 Hz), 21.56 (d, J C-P = 3.0Hz).FT-IR (KBr): 3055, 3025, 2922, 1674, 1596, 1496, 1445, 1409, 1271, 1179,1131, 1081, 1029, 1000, 834, 804, 752, 697, 562, 552, 518, 447, 418 cm -1 HRMS(ESI)calcd for C 25 H 26 OP + [M+H] + 373.1716, found 373.1721.

[0082] The characterization data of compound II-8 are as follows:

[0083]

[0084] White solid (1.6 g, 37% yield). Melting point: 101.6–105.6 °C. 31 P{ 1 H} NMR (202MHz, CDCl3)δ 34.94. 19 F NMR (471 MHz, CDCl3)δ –63.19. 1 H NMR (500 MHz, CDCl3)δ7.55 (dd, J= 10.6, 8.0 Hz, 2H), 7.39 (dd, J = 8.3, 2.3 Hz, 2H), 7.22 – 7.13 (m,10H), 5.35 (d, J = 4.6 Hz, 2H), 5.17 (d, J = 4.7 Hz, 2H), 3.31 – 3.13 (m, 4H). 13 CNMR (126 MHz, CDCl3)δ 140.67 (d, J C-P = 3.1 Hz), 138.50 (d, J C-P = 9.0 Hz), 135.62(d, J C-P = 91.6 Hz), 132.96 (qd, J C-F = 32.3, J C-P = 2.5 Hz), 131.46 (d, J C-P = 9.1 Hz),128.29, 127.75, 126.23, 124.56(q, J C-F = 273.7 Hz), 124.49 (dq, J C-P = 11.4 Hz, J C-F =3.5 Hz), 118.04 (d, J C-P = 9.1 Hz), 37.09 (d, J C-P = 63.6 Hz). FT-IR (KBr): 3091,3053, 2958, 2910, 1615, 1601, 1574, 1497, 1445, 1415, 1399, 1329, 1242, 1220,1193, 1162, 1127, 1101, 1061, 1029, 1018, 1000, 944, 901, 844, 829, 778, 751,731, 703, 630, 616, 598, 591, 528, 496, 443, 416 cm -1 . HRMS (ESI)calcd forC 25 H23 F3OP + [M+H] + 427.1433, found 427.1439.

[0085] The characterization data for compound II-9 are as follows:

[0086]

[0087] Colorless oil (2.0 g, 56% yield). 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 34.33. 1 HNMR (500 MHz, CDCl3) δ 7.79 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H), 7.61(d, J = 8.2 Hz, 2H), 7.39 (dt, J = 20.0, 7.1 Hz, 4H), 7.24 – 7.15 (m, 5H), 7.03 –6.96 (m, 4H), 5.54 (d, J = 4.4 Hz, 2H), 5.25 (d, J = 4.4 Hz, 2H), 3.28 (t, J = 15.3Hz, 2H), 3.10 (dd, J = 14.7, 11.3 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 140.28 (d, J C-P = 3.3 Hz), 138.12 (d, J C-P = 9.2 Hz), 133.59, 131.40, 131.11 (d, J C-P = 2.8 Hz), 130.66 (d, J C-P = 9.0 Hz), 130.45, 128.40, 127.71 (d, J C-P = 2.6 Hz), 127.60,126.00, 125.78, 125.65, 125.34, 125.16, 121.39 (d,J C-P = 8.8 Hz), 39.70 (d, J C-P =62.8 Hz). FT-IR (neat):3055, 1630, 1590, 1507, 1437, 1399, 1339, 1294, 1254,1190, 1111, 1069, 1025, 1006, 907, 847, 802, 777, 727, 694, 660, 642, 617,594, 571, 542, 513, 492, 467, 437, 423, 410 cm -1 HRMS (ESI)calcd for C 32 H 28 OP + [M+H] + 459.1872, found 459.1870.

[0088] The characterization data of compound II-10 are as follows:

[0089]

[0090] Colorless oil (1.5 g, 35% yield). 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 35.76. 1 HNMR (500 MHz, CDCl3)δ 7.52 (dd, J = 10.5, 7.8 Hz, 2H), 7.36 (dd, J = 7.6, 1.7 Hz,1H), 7.29 – 7.26 (m, 2H), 6.84 (d, J = 8.9 Hz, 6H), 5.34 (d, J = 4.4 Hz, 2H), 5.16 (d, J = 4.4 Hz, 2H), 3.25 – 3.09 (m, 4H), 2.24 (s, 12H). 13 C NMR (126 MHz, CDCl3)δ 141.28 (d, J C-P = 3.6 Hz), 139.12 (d, J C-P= 8.7 Hz), 137.79, 131.71 (d, J C-P = 94.8 Hz), 131.40 (d, J C-P = 2.9 Hz), 131.10 (d, J C-P = 8.8 Hz), 129.42, 127.90 (d, J C-P = 11.6 Hz), 124.28, 117.49 (d, J C-P = 8.8 Hz), 37.21 (d, J C-P = 63.7 Hz),21.37. FT-IR (neat): 2915, 2863, 1673, 1598, 1436, 1402, 1377, 1308, 1264,1239, 1177, 1111, 1070, 1039, 998, 946, 895, 847, 733, 694, 638, 612, 593,567, 545, 503, 436, 413 cm -1 HRMS (ESI)calcd for C 28 H 32 OP + [M+H] + 415.2185, found415.21854.

[0091] The characterization data of compound II'-1 are as follows:

[0092]

[0093] White solid (1.2 g, 30% yield). Melting point: 74.2 – 80.3 °C. 31 P{ 1 H} NMR (202MHz, CDCl3) δ 42.81. 1 H NMR (500 MHz, CDCl3)δ 7.28 – 7.23 (m, 15H), 5.42 (dd, J =4.2, 0.9 Hz, 3H), 5.24 (d, J = 4.1 Hz, 3H), 2.82 (d, J = 14.5 Hz, 6H). 13C NMR (126MHz, CDCl3)δ 141.03 (d, J C-P = 3.5 Hz), 139.14 (d, J C-P = 8.1 Hz), 128.64, 128.05,126.32, 117.94 (d, J C-P = 8.8 Hz), 35.12 (d, J C-P = 60.7 Hz). FT-IR (neat):3058,3024, 2914, 1675, 1615, 1598, 1573, 1494, 1443, 1411, 1377, 1301, 1276, 1219,1183, 1140, 1070, 1028, 985, 942, 898, 858, 776, 725, 699, 621, 611, 555,522, 504, 484, 449, 422 cm -1 .HRMS (ESI)calcd for C 27 H 28 OP + [M+H] + 399.1872, found 399.1870.

[0094] Example 2 Synthesis of organophosphorus compound II-S1

[0095]

[0096] Step S4: In a 25 mL round-bottom flask, add diallyl organophosphorus compound II (1 mmol) and Lawson's reagent (0.6 mmol) sequentially. Vacuum the mixture five times under argon purging, then add tetrahydrofuran (10 mL). The reaction is then carried out at 80 °C for 12 hours. After the reaction is complete, concentrate the mixture under reduced pressure and purify it by column chromatography using petroleum ether:ethyl acetate at a ratio of 50:1 to obtain compound II-S1.

[0097] The characterization data of compound II-S1-1 are as follows:

[0098]

[0099] Yellow oily substance (269 mg, 72% yield). 31 P{ 1 H} NMR (162 MHz, CDCl3)δ 45.31.1 HNMR (400 MHz, CDCl3)δ 7.55 (dd, J = 12.7, 7.2 Hz, 2H), 7.20 (dd, J = 7.5, 1.7 Hz,1H), 7.13 – 7.06 (m, 12H), 5.26 (d, J = 5.3 Hz, 2H), 5.04 (d, J = 5.3 Hz, 2H),3.32 – 3.16 (m, 4H). 13 C NMR (100 MHz, CDCl3)δ 141.13 (d, J C-P = 3.2 Hz), 138.93(d, J C-P = 9.1 Hz), 131.62 (d, J C-P = 9.8 Hz), 131.27 (d, J C-P = 3.0 Hz), 130.05 (d, J C-P = 74.8 Hz), 128.28, 127.84 (d, J C-P = 11.9 Hz), 127.65, 126.55 (d, J C-P = 1.5Hz), 118.71 (d, J C-P = 10.0 Hz), 40.49 (d, J C-P = 48.1 Hz).FT-IR (KBr): 3054, 3024,2919, 1674, 1493, 1444, 1436, 1401, 1302, 1272, 1181, 1158, 1105, 1070, 1027,999, 902, 862, 776, 745, 693, 629, 613, 485 cm -1 .HRMS (ESI)calcd for C 24 H 24 PS + [M+H] + 375.1331, found 375.1330.

[0100] Example 3 Synthesis of phosphorus-heterocyclic organophosphorus compounds III and III'

[0101]

[0102] Specific experimental procedures: In a 10 mL sealed tube, add diallyl organophosphorus compound II or II' or II-S1 (0.2 mmol) and 10-phenylphenthiazide (0.01 mmol) sequentially. Vacuum the tube five times under argon purging, and then add acetonitrile (3 mL) while maintaining purging. Seal the reaction system. React at room temperature for 2 hours under 390 nm illumination. After the reaction is complete, concentrate under reduced pressure and purify by column chromatography using petroleum ether:ethyl acetate in a 1:1 ratio to obtain compound III or III'.

[0103] The characterization data of compound III-1 are as follows:

[0104]

[0105] White solid (65 mg, 90% yield, dr 9.4 / 1). Melting point: 194.6 – 196.9 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 67.14. 1 H NMR (400 MHz, CDCl3) δ 8.03 (ddd, J = 11.4, 6.7,3.0 Hz, 2H), 7.58 (dt, J = 4.2, 2.4 Hz, 3H), 7.22 (dd, J = 7.6, 1.8 Hz, 4H), 7.09(dd, J = 8.5, 6.8 Hz, 4H), 7.03 – 6.97 (m, 2H), 2.99 – 2.80 (m, 6H), 2.14 (q, J =6.2 Hz, 2H). 13 C NMR (100 MHz, CDCl3)δ 142.83 (d, J C-P = 7.0 Hz), 133.26 (d, J C-P =90.2 Hz), 132.00 (d, J C-P = 2.7 Hz), 130.35 (d, J C-P= 9.5 Hz), 128.90 (d, J C-P = 11.4Hz), 127.71, 127.09, 125.93, 58.44 (d, J C-P = 9.8 Hz), 45.63 (d, J C-P = 65.3 Hz), 29.73 (d, J = 5.4 Hz). FT-IR (neat): 3047, 3022, 2956, 1599, 1501, 1486, 1443,1436, 1411, 1401, 1300, 1244, 1227, 1215, 1196, 1173, 1143, 1106, 1075, 1035,999, 983, 956, 923, 910, 901, 858, 835, 804, 763, 742, 729, 697, 637, 619,574, 554, 509, 480, 457, 429, 421, 412, 403 cm -1 HRMS (ESI)calcd for C 24 H 24 OP + [M+H] + 359.1559, found 359.1557.

[0106] Table 1 Single crystal data of compound III-1

[0107]

[0108] The characterization data of compound III'-1 are as follows:

[0109]

[0110] White solid (64 mg, 80% yield, dr 8.6 / 1). Melting point: 84.5 – 86.7 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 76.00. 1 H NMR (500 MHz, CDCl3)δ 7.59 – 7.55 (m, 2H),7.39 (dd, J = 8.4, 6.7 Hz, 2H), 7.32 (t, J= 7.4 Hz, 1H), 7.09 – 7.02 (m, 8H),7.01 – 6.96 (m, 2H), 5.66 (d, J = 4.5 Hz, 1H), 5.48 (d, J = 4.7 Hz, 1H), 3.56 (d, J = 15.7 Hz, 2H), 2.73 (q, J = 6.1 Hz, 2H), 2.58 (t, J = 16.4 Hz, 2H), 2.45 (dd, J =16.4, 4.0 Hz, 2H), 1.88 (q, J = 6.2 Hz, 2H). 13 C NMR (126 MHz, CDCl3)δ 142.76 (d, J C-P = 7.2 Hz), 140.21 (d, J C-P = 1.9 Hz), 140.04 (d, J C-P = 8.3 Hz), 128.94, 128.51,127.81, 127.13, 126.52, 126.02, 117.89 (d, J C-P = 9.2 Hz), 58.38 (d, J C-P = 9.5Hz), 43.68 (d, J C-P = 62.3 Hz), 39.16 (d, J C-P = 55.4 Hz), 29.41 (d, J C-P = 5.2 Hz).FT-IR (neat): 3055, 3021, 2954, 2922, 1709, 1676, 1618, 1599, 1580, 1445,1405, 1301, 1270, 1225, 1181, 1167, 1142, 1114, 1074, 1030, 1014, 959, 910,866, 827, 799, 780, 762, 746, 693, 608, 595, 538, 524, 498, 477, 425 cm -1.HRMS (ESI)calcd for C 27 H 28 OP + [M+H] + 399.1872, found 399.1871.

[0111] The characterization data of compound III-2 are as follows:

[0112]

[0113] White solid (76 mg, 97% yield, dr 21.1 / 1). Melting point: 124.1 – 128.1 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 63.68. 1 H NMR (400 MHz, CDCl3)δ 8.11 (ddd, J = 12.7, 7.6,1.8 Hz, 1H), 7.56 (td, J = 8.0, 1.7 Hz, 1H), 7.26 (dd, J = 7.7, 1.7 Hz, 4H), 7.16(td, J = 7.4, 1.7 Hz, 1H), 7.07 (t, J = 7.7 Hz, 4H), 7.03 – 6.95 (m, 3H), 3.97(s, 3H), 3.08 (dd, J = 15.8, 6.0 Hz, 2H), 2.85 (q, J = 6.2 Hz, 2H), 2.75 (t, J =16.2 Hz, 2H), 2.22 (q, J = 6.3 Hz, 2H). 13 C NMR (100 MHz, CDCl3)δ 159.85 (d, J C-P =4.2 Hz), 143.34 (d, J C-P = 6.2 Hz), 134.52 (d, J C-P = 6.1 Hz), 134.18 (d, J C-P= 2.2Hz), 127.48, 127.30, 125.61, 121.17 (d, J C-P = 10.7 Hz), 119.67 (d, J C-P = 88.4Hz), 110.82 (d, J C-P = 6.4 Hz), 58.45 (d, J C-P = 10.2 Hz), 55.31, 44.27 (d, J C-P =67.0 Hz), 29.36 (d, J C-P = 6.5 Hz). FT-IR (neat): 3058, 2965, 2930, 1589, 1576,1498, 1477, 1463, 1445, 1432, 1400, 1342, 1298, 1274, 1241, 1212, 1185, 1175,1165, 1142, 1118, 1045, 1032, 1014, 960, 944, 919, 905, 872, 828, 798, 757,726, 696, 642, 620, 573, 513, 492, 461, 427cm -1 HRMS (ESI)calcd for C 25 H 26 O2P + [M+H] + 389.1665, found 389.1664.

[0114] The characterization data of compound III-3 are as follows:

[0115]

[0116] White solid (65 mg, 84% yield, dr 7 / 1). Melting point: 124.0 – 127.3 °C. 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 67.14. 1 H NMR (500 MHz, CDCl3)δ 7.60 (dd, J= 12.3, 2.4 Hz,1H), 7.56 – 7.48 (m, 2H), 7.21 (d, J = 7.9 Hz, 4H), 7.15 – 7.08 (m, 5H), 7.02(t, J = 7.3 Hz, 2H), 3.90 (d, J = 1.3 Hz, 3H), 2.94 (t, J = 16.6 Hz, 2H), 2.90 –2.82 (m, 4H), 2.16 (q, J = 6.2 Hz, 2H). 13 C NMR (126 MHz, CDCl3)δ 159.94 (d, J C-P =13.8 Hz), 142.89 (d, J C-P = 7.0 Hz), 134.74 (d, J C-P = 89.4 Hz), 130.29 (d, J C-P =13.4 Hz), 127.84, 127.20, 126.06, 122.07 (d, J C-P = 9.8 Hz), 118.12 (d, J C-P = 2.5Hz), 115.90 (d, J C-P = 10.1 Hz), 58.60 (d, J C-P = 9.8 Hz), 55.58, 45.81 (d, J C-P =65.5 Hz), 29.84 (d, J C-P= 5.4 Hz). FT-IR (neat): 3056, 3021, 2923, 2869, 1590,1573, 1479, 1459, 1445, 1419, 1341, 1313, 1284, 1231, 1213, 1197, 1188, 1117,1078, 1041, 941, 919, 900, 861, 820, 794, 757, 724, 698, 691, 635, 619, 571,560, 506, 482, 453, 426, 414, 403cm -1 HRMS (ESI)calcd for C 25 H 26 O2P + [M+H] + 389.1665, found 389.1664.

[0117] The characterization data of compound III-4 are as follows:

[0118]

[0119] Yellow solid (66 mg, 85% yield, dr 9 / 1). Melting point: 181.1 – 184.6 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 66.73. 1 H NMR (500 MHz, CDCl3)δ 7.94 (dd, J = 10.9, 8.4Hz, 2H), 7.20 (d, J = 7.7 Hz, 4H), 7.12 – 7.06 (m, 6H), 7.01 (td, J = 7.2, 1.4Hz, 2H), 3.87 (d, J = 2.1 Hz, 3H), 2.91 (t, J = 16.7 Hz, 2H), 2.87 – 2.79 (m,4H), 2.13 (q, J = 6.2 Hz, 2H). 13 C NMR (126 MHz, CDCl3)δ 162.61 (d, J C-P = 2.9 Hz), 143.07 (d, JC-P = 7.2 Hz), 132.29 (d, J C-P = 10.7 Hz), 127.78, 127.16, 125.97,124.31 (d, J C-P = 96.4 Hz), 114.55 (d, J C-P = 12.2 Hz), 58.35 (d, J C-P = 9.8 Hz), 55.45, 45.76 (d, J C-P = 65.8 Hz), 29.82 (d, J C-P = 5.2 Hz).FT-IR (neat):3064, 2984,2948, 1594, 1568, 1503, 1458, 1436, 1409, 1310, 1294, 1259, 1208, 1189, 1172,1147, 1135, 1106, 1079, 1069, 1050, 1025, 941, 917, 889, 860, 830, 822, 800,762, 734, 710, 696, 646, 630, 572, 554, 513, 469, 424 cm -1 HRMS (ESI) calcd for C 25 H 26 O2P + [M+H] + 389.1665, found 389.1664.

[0120] The characterization data for compound III-5 are as follows:

[0121]

[0122] White solid (71 mg, 83% yield, dr 7.4 / 1). Melting point: 121.6 – 126.9 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 65.62. 1 H NMR (400 MHz, CDCl3) δ 8.17 (dd, J = 10.9, 8.0Hz, 2H), 7.87 (dd,J = 8.3, 2.2 Hz, 2H), 7.21 (dd, J = 7.6, 1.7 Hz, 4H), 7.12(dd, J = 8.5, 6.7 Hz, 4H), 7.07 – 7.02 (m, 2H), 3.05 – 2.91 (m, 4H), 2.87 (dd, J = 16.4, 4.5 Hz, 2H), 2.16 (q, J = 6.2 Hz, 2H). 13 C NMR (100 MHz, CDCl3)δ 142.55(d, J C-P = 7.0 Hz), 137.80 (d, J C-P = 86.6 Hz), 134.04 (dd, J C-F = 33.0 Hz, J C-P = 2.9Hz), 131.14 (d, J C-P = 9.8 Hz), 127.98, 127.21, 126.36 126.29 (q, J C-F = 272.9 Hz),125.95 (dq, J C-P = 11.4 Hz, J C-F = 3.7 Hz), 58.74 (d, J C-P = 10.1 Hz), 45.83 (d, J C-P =65.7 Hz), 30.01 (d, J C-P= 5.7 Hz). FT-IR (neat):3058, 3023, 2924, 1597, 1573,1499, 1479, 1459, 1445, 1397, 1324, 1285, 1215, 1197, 1164, 1149, 1127, 1103,1078, 1062, 1042, 1015, 957, 942, 919, 904, 861, 845, 825, 794, 758, 737,725, 695, 636, 597, 573, 562, 500, 453, 433, 417cm -1 HRMS (ESI)calcd for C 25 H 23 F3OP + [M+H] + 427.1433, found 427.1432.

[0123] The characterization data for compound III-6 are as follows:

[0124]

[0125] White solid (67 mg, 90% yield, dr 19.2 / 1). Melting point: 103.9 – 108.1 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 67.27. 1 H NMR (400 MHz, CDCl3)δ 7.82 (dd, J = 12.4, 7.5Hz, 1H), 7.51 – 7.46 (m, 1H), 7.36 (ddd, J = 10.7, 8.1, 5.5 Hz, 2H), 7.17 (d, J =7.7 Hz, 4H), 7.11 (dd, J = 8.6, 6.7 Hz, 4H), 7.06 – 7.01 (m, 2H), 3.14 – 2.97(m, 4H), 2.81 (s, 3H), 2.72 (q, J = 6.1 Hz, 2H), 2.00 (q, J = 6.2 Hz, 2H). 13 C NMR(100 MHz, CDCl3)δ 143.40 (d,J C-P = 8.7 Hz), 141.70 (d, J C-P = 7.6 Hz), 133.10 (d, J C-P = 89.9 Hz), 132.16 (d, J C-P = 3.1 Hz), 132.10 (d, J C-P = 4.3 Hz), 129.84 (d, J C-P =11.4 Hz), 127.87, 127.01, 126.06, 125.81 (d, J C-P = 11.6 Hz), 57.47 (d, J C-P = 9.7Hz), 44.49 (d, J C-P = 65.4 Hz), 29.48 (d, J C-P = 4.1 Hz), 21.84 (d, J C-P = 4.3 Hz).FT-IR (neat):3055, 3021, 2983, 2924, 1591, 1497, 1444, 1401, 1376, 1340,1247, 1221, 1188, 1163, 1146, 1134, 1082, 1033, 950, 936, 859, 825, 753, 715,699, 640, 619, 572, 558, 524, 500, 445, 414 cm -1 HRMS (ESI)calcd for C 25 H 26 OP + [M+H] + 373.1716, found 373.1713.

[0126] The characterization data for compound III-7 are as follows:

[0127]

[0128] Colorless oil (69 mg, 85% yield, dr 13 / 1). 31 P{1 H} NMR (162 MHz, CDCl3) δ67.11. 1 H NMR (400 MHz, CDCl3)δ 8.77 (d, J = 8.4 Hz, 1H), 8.11 (dd, J = 13.9, 7.3Hz, 2H), 7.97 (d, J = 8.2 Hz, 1H), 7.68 (t, J = 7.6 Hz, 1H), 7.65 – 7.56 (m, 2H),7.20 (d, J = 7.3 Hz, 4H), 7.13 (t, J = 7.5 Hz, 4H), 7.06 (dd, J = 8.3, 6.2 Hz, 2H),3.26 (dd, J = 16.4, 5.9 Hz, 2H), 3.18 (t, J = 16.8 Hz, 2H), 2.68 (q, J = 6.1 Hz,2H), 1.96 (q, J = 6.2 Hz, 2H). 13 C NMR (100 MHz, CDCl3)δ 143.60 (d, J C-P = 9.2 Hz),134.12 (d, J C-P = 8.6 Hz), 133.32 (d, J C-P = 2.8 Hz), 133.00 (d, J C-P = 7.6 Hz),131.48 (d, J C-P = 88.8 Hz), 129.33 (d, J C-P = 10.4 Hz), 129.31, 127.97, 127.90,127.01, 126.94, 126.73 (d, J C-P = 5.5 Hz), 126.14, 124.61 (d, J C-P = 13.1 Hz),57.49 (d, JC-P = 9.9 Hz), 44.75 (d, J C-P = 65.7 Hz), 29.48 (d, J C-P = 3.7 Hz). FT-IR(neat):3055, 2978, 1731, 1676, 1590, 1493, 1459, 1441, 1401, 1371, 1339,1299, 1240, 1183, 1138, 1075, 1027, 985, 903, 847, 832, 801, 774, 756, 697,635, 619, 608, 574, 559, 538, 503, 439, 406 cm -1 HRMS (ESI)calcd for C 28 H 26 OP + [M+H] + 409.1716, found 409.1714.

[0129] The characterization data for compound III-8 are as follows:

[0130]

[0131] White solid (60 mg, 80% yield, dr 7 / 1). Melting point: 122.4–127.7 °C. 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 64.92. 1 H NMR (400 MHz, CDCl3)δ 8.10 (ddd, J = 12.6, 6.6, 3.0Hz, 2H), 7.62 – 7.55 (m, 3H), 7.18 – 7.09 (m, 8H), 7.08 – 7.02 (m, 2H), 3.40(dd, J = 16.2, 6.9 Hz, 2H), 3.16 (t, J = 15.8 Hz, 2H), 2.69 (q, J = 6.2 Hz, 2H), 2.11 (q, J = 6.3 Hz, 2H). 13 C NMR (100 MHz, CDCl3)δ 143.35 (d,J C-P = 10.1 Hz), 135.31 (d, J C-P = 71.5 Hz), 131.64 (d, J C-P = 3.0 Hz), 129.91 (d, J C-P = 9.9 Hz), 129.18 (d, J C-P = 11.6 Hz), 127.86, 127.11, 126.16, 59.80 (d, J C-P = 7.5 Hz), 49.96(d, J C-P = 50.8 Hz), 29.35 (d, J C-P = 3.1 Hz). FT-IR (neat): 3052, 3022, 2981,1599, 1498, 1444, 1433, 1406, 1320, 1243, 1197, 1182, 1155, 1077, 1061, 1029,1000, 955, 926, 898, 826, 792, 779, 761, 693, 677, 642, 631, 617, 602, 567,532, 499, 478, 426, 405 cm -1 .HRMS (ESI)calcd for C 24 H 24 PS + [M+H] + 375.1331, found 375.1328.

[0132] The characterization data for compound III-9 are as follows:

[0133]

[0134] White solid (69 mg, 86% yield, dr 8.7 / 1). Melting point: 137.2 – 141.4 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 66.43. 1 H NMR (400 MHz, CDCl3)δ 7.55 (ddd, J= 11.9, 7.9,1.5 Hz, 1H), 7.42 (dd, J = 10.8, 1.5 Hz, 1H), 7.20 (d, J = 7.3 Hz, 4H), 7.09 (t, J = 7.5 Hz, 4H), 7.01 (dd, J = 8.1, 6.0 Hz, 3H), 6.05 (s, 2H), 2.96 – 2.84 (m,4H), 2.79 (dd, J = 16.3, 4.9 Hz, 2H), 2.14 (q, J = 6.2 Hz, 2H). 13 C NMR (100 MHz,CDCl3) δ 151.01 (d, J C-P = 2.9 Hz), 148.45 (d, J C-P = 17.3 Hz), 142.96 (d, J C-P = 7.2Hz), 127.83, 127.19, 126.35 (d, J C-P = 93.9 Hz), 126.04, 125.77 (d, J C-P = 10.4Hz), 109.98 (d, J C-P = 12.4 Hz), 109.10 (d, J C-P = 14.3 Hz), 101.83, 58.42 (d, J C-P =10.0 Hz), 45.85 (d, J C-P = 66.0 Hz), 29.90 (d, J C-P= 5.3 Hz). FT-IR (neat):3041,2962, 1597, 1505, 1485, 1474, 1445, 1420, 1403, 1341, 1265, 1242, 1211, 1194,1181, 1118, 1061, 1041, 954, 933, 921, 903, 881, 859, 825, 799, 759, 746,697, 639, 596, 584, 566, 547, 502, 472, 457, 436, 430, 411 cm -1 HRMS (ESI)calcd for C 25 H 24 O3P + [M+H] + 403.1458 was found; 403.1456 was also found.

[0135] The characterization data of compound III-10 are as follows:

[0136]

[0137] Colorless oil (65 mg, 87% yield, dr 9 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ75.57. 1 H NMR (400 MHz, CDCl3) δ 7.44 – 7.37 (m, 4H), 7.32 (ddq, J = 8.3, 5.5,1.9 Hz, 1H), 7.10 – 7.03 (m, 8H), 7.02 – 6.96 (m, 2H), 3.61 (d, J = 14.8 Hz, 2H), 2.69 (q, J = 6.3 Hz, 2H), 2.66 – 2.56 (m, 4H), 1.75 (q, J = 6.2 Hz, 2H). 13 CNMR (100 MHz, CDCl3)δ 142.94 (d, J C-P = 7.7 Hz), 132.55 (d, J C-P = 7.4 Hz), 129.90(d, J C-P= 5.1 Hz), 129.18 (d, J C-P = 2.6 Hz), 127.83, 127.39 (d, J C-P = 3.1 Hz),127.03, 126.03, 58.14 (d, J C-P = 9.6 Hz), 42.97 (d, J C-P = 62.4 Hz), 39.89 (d, J C-P =55.4 Hz), 29.30 (d, J C-P = 4.7 Hz). FT-IR (neat):3058, 2962, 1600, 1495, 1445,1402, 1340, 1266, 1240, 1218, 1196, 1158, 1118, 1074, 1031, 1010, 955, 922,903, 828, 797, 758, 695, 584, 565, 536, 501, 472, 429 cm -1 .HRMS (ESI)calcd for C 25 H 26 OP + [M+H] + 373.1716, found 373.1715.

[0138] The characterization data of compound III-11 are as follows:

[0139]

[0140] White solid (62 mg, 80% yield, dr 7.5 / 1). Melting point: 177.0 – 180.8 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 66.45. 1 H NMR (500 MHz, CDCl3) δ 8.02 (ddd, J = 11.0, 6.6,2.2 Hz, 2H), 7.63 – 7.56 (m, 3H), 7.10 (d, J = 8.0 Hz, 4H), 6.93 (d, J= 7.9 Hz,4H), 2.95 – 2.79 (m, 6H), 2.22 (s, 6H), 2.12 (q, J = 6.2 Hz, 2H). 13 C NMR (126MHz, CDCl3)δ 140.21 (d, J C-P = 7.3 Hz), 135.47, 133.58 (d, J C-P = 89.9 Hz), 132.04(d, J C-P = 2.8 Hz), 130.46 (d, J C-P = 9.4 Hz), 128.99 (d, J C-P = 11.4 Hz), 128.56,127.12, 58.06 (d, J C-P = 9.9 Hz), 45.82 (d, J C-P = 65.5 Hz), 29.98 (d, J C-P = 5.3 Hz),20.90. FT-IR (neat):2967, 2919, 1590, 1517, 1438, 1397, 1221, 1210, 1195,1176, 1148, 1107, 1070, 1019, 947, 932, 917, 866, 834, 819, 804, 785, 747,726, 719, 696, 611, 571, 552, 513, 483, 440, 407 cm -1 .HRMS (ESI)calcd for C 26 H 28 OP + [M+H] + 387.1872, found 387.1871.

[0141] The characterization data of compound III-12 are as follows:

[0142]

[0143] White solid (65 mg, 76% yield, dr 6.6 / 1). Melting point: 216.3 – 221.7 °C.31 P{ 1 H}NMR (202 MHz, CDCl3) δ 66.78. 1 H NMR (500 MHz, CDCl3)δ 7.98 (dd, J = 11.0, 7.4Hz, 2H), 7.63 – 7.55 (m, 3H), 7.15 (d, J = 8.5 Hz, 4H), 7.09 (d, J = 8.4 Hz, 4H),2.88 – 2.78 (m, 6H), 2.17 (q, J = 6.2 Hz, 2H). 13 C NMR (126 MHz, CDCl3)δ 141.20(d, J C-P = 6.5 Hz), 132.57 (d, J C-P = 90.9 Hz), 132.37 (d, J C-P = 2.8 Hz), 132.23,130.50 (d, J C-P = 9.6 Hz), 129.13 (d, J C-P = 11.6 Hz), 128.73, 128.12, 58.35 (d, J C-P = 9.6 Hz), 45.90 (d, J C-P = 65.2 Hz), 30.05 (d, J C-P = 5.9 Hz). FT-IR (neat):2988,2944, 1491, 1463, 1450, 1435, 1407, 1310, 1216, 1140, 1119, 1104, 1094, 1008,956, 945, 871, 858, 847, 827, 819, 809, 797, 764, 732, 718, 707, 697, 575,564, 530, 511, 485, 474, 463, 437, 420, 403 cm -1 . HRMS (ESI)calcd forC 24 H 22 Cl2OP+ [M+H] + 427.0780, found 427.0778.

[0144] The characterization data of compound III-13 are as follows:

[0145]

[0146] Brown solid (38 mg, 42% yield, dr>20 / 1). Melting point: 213.5 – 218.1 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 61.71. 1 H NMR (500 MHz, CDCl3) δ 8.12 (dd, J = 12.3, 7.9Hz, 4H), 7.90 (dd, J = 7.8, 1.7 Hz, 2H), 7.74 (d, J = 8.1 Hz, 2H), 7.66 – 7.60(m, 3H), 7.55 – 7.43 (m, 6H), 7.20 (t, J = 7.8 Hz, 2H), 3.53 (dd, J = 16.5, 4.6Hz, 2H), 3.06 (t, J = 16.8 Hz, 2H), 2.98 – 2.90 (m, 2H), 2.87 – 2.78 (m, 2H). 13 CNMR (126 MHz, CDCl3) δ 140.61 (d, J C-P = 7.4 Hz), 134.77, 134.12 (d, J C-P = 91.6Hz), 131.89 (d, J C-P = 2.8 Hz), 130.61, 130.29 (d, J C-P = 9.2 Hz), 129.45, 128.96 (d, J C-P = 11.4 Hz), 127.56, 126.86, 125.44, 125.20, 125.09, 124.33, 58.93 (d, JC-P = 9.9 Hz), 45.78 (d, J C-P = 63.8 Hz), 34.26 (d, J C-P = 5.9 Hz).FT-IR (neat):3053, 2921, 1594, 1574, 1507, 1436, 1393, 1339, 1258, 1224, 1199, 1182, 1135,1111, 1067, 1016, 998, 938, 924, 887, 859, 847, 809, 801, 780, 763, 747, 732,696, 665, 652, 635, 615, 584, 577, 567, 535, 517, 493, 474, 466, 440, 411cm -1 HRMS (ESI)calcd for C 32 H 28 OP + [M+H] + 459.1872, found 459.1872.

[0147] The characterization data of compound III-14 are as follows:

[0148]

[0149] White solid (76 g, 92% yield, dr 3.5 / 1). Melting point: 139.4–143.3 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 67.71. 1 H NMR (500 MHz, CDCl3) δ 8.04 (ddd, J = 11.2, 6.7,2.5 Hz, 2H), 7.65 – 7.55 (m, 3H), 6.82 (s, 4H), 6.67 (s, 2H), 2.94 (t, J = 16.8Hz, 2H), 2.83 (dt, J = 18.6, 5.5 Hz, 4H), 2.16 (s, 12H), 2.09 (q, J = 6.2 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 142.96 (d, J C-P = 7.6 Hz), 137.02, 133.79 (d, J C-P =89.8 Hz), 132.07 (d, J C-P = 2.7 Hz), 130.48 (d, J C-P = 9.4 Hz), 129.04 (d, J C-P = 11.4Hz), 127.54, 125.14, 58.39 (d, J C-P = 9.8 Hz), 45.45 (d, J C-P = 65.4 Hz), 29.73 (d, J C-P = 4.8 Hz), 21.37. FT-IR (neat):3002, 2912, 1601, 1463, 1437, 1406, 1375,1308, 1233, 1212, 1187, 1169, 1153, 1108, 1069, 1036, 995, 952, 930, 890,877, 850, 815, 798, 753, 737, 705, 693, 676, 613, 580, 542, 520, 488, 470,436 cm -1 HRMS (ESI)calcd for C 28 H 32 OP + [M+H] + 415.2185, found 415.21854.

[0150] Application example: Phosphorus-bicyclic [3,2,0] organophosphorus compounds were used as catalysts to catalyze the chlorination reaction of primary alcohols to synthesize compound 2.

[0151]

[0152] Experimental procedure: Weigh the catalyst (0.01 mmol) into a 10 mL sealed tube containing argon gas. After purging five times with argon gas, add ultra-dry toluene (1 mL), phenylethanol (0.2 mmol), phenylsilane (0.2 mmol), and hexachloroacetone (0.14 mmol) sequentially. Seal the reaction system and react at 100 °C for 24 hours. After the reaction is complete, wash with water, extract with ethyl acetate, dry, filter, concentrate under reduced pressure, and purify the concentrate by column chromatography with petroleum ether.

[0153] Following the steps described above, this invention selects various types of phosphorus heterobicyclic [3,2,0] organophosphorus compounds as catalysts to demonstrate the structure-activity relationship between catalyst substituent type and catalytic effect in the Appel catalytic reaction for the preparation of chlorinated hydrocarbons from primary alcohols. The catalytic results are shown in the table below:

[0154] Table 2. Structure-activity relationship between substituent type and catalytic effect in the chlorination reaction of primary alcohols using phosphatic bicyclic [3,2,0] organophosphorus compounds.

[0155]

[0156] The catalytic reaction results described in the table demonstrate that the phosphabicyclic [3,2,0] organophosphorus compound can achieve good catalytic performance as a catalyst in the Appel reaction of primary alcohols to chlorinated hydrocarbons, and various skeletal structures are applicable. Compared with previously reported organophosphorus compounds as catalysts [J. Org. Chem. 2019, 84, 7863−7870], which require 10 mol% organophosphorus compound as catalyst to achieve the Appel reaction of phenylethanol under the same substrate conditions, the phosphabicyclic [3,2,0] organophosphorus compound in this application is reduced to 5 mol% catalyst, and the amount of chloride is also reduced, resulting in a yield that is superior to that reported in the literature.

[0157] To further verify the high efficiency of the phosphabicyclic [3,2,0] organophosphorus compound in this application for catalyzing the chlorination reaction of primary alcohols, a comparative catalytic performance experiment was conducted with a previously filed multi-substituted phosphabicyclic six-membered ring organophosphorus compound containing trifluoromethyl (202511080347.6) and a phosphabicyclic bridged ring organophosphorus compound containing trifluoromethyl. The compounds in the aforementioned patent applications all exhibited lower catalytic activity, and their efficiency in catalyzing the chlorination reaction of primary alcohols was significantly lower than that of the compound provided in this invention.

[0158]

[0159]

[0160] The above results indicate that the phosphabicyclic [3,2,0] organophosphorus compound catalyst in this application possesses excellent catalytic performance, demonstrating the significant advantages of phosphabicyclic [3,2,0] skeleton organophosphorus compounds in primary alcohol chlorination reactions. The phosphabicyclic [3,2,0] skeleton organophosphorus compounds reported in this invention have better preparation versatility and scalability, making the further development of this type of phosphine oxide catalyst with good prospects and scalability in catalyst synthesis, laying a good foundation for further exploration of the development and application of various types of phosphabicyclic organophosphorus compound catalysts.

[0161] Obviously, the specific implementation schemes described above are merely a further detailed explanation of the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above descriptions are only specific examples of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A phosphorus-biscyclic [3,2,0] organophosphorus compound, characterized in that, The general structural formula of the phosphorohexacyclic [3,2,0] organophosphorus compound is shown in any of the following: 、 ； Where X is an oxygen atom or a sulfur atom; Ar 1 It is a benzene ring, benzodioxane, or naphthalene ring; n is 0, 1, or 2; R 1 It is hydrogen, trifluoromethyl, C1-C6 alkoxy or C1-C6 saturated alkyl; R 2 It is a C1-C6 saturated alkyl, naphthyl, phenyl, or substituted phenyl; a substituted phenyl is a phenyl in which the hydrogen atom is replaced by a halogen atom or a C1-C6 saturated alkyl group.

2. The phosphorus-heterocyclic [3,2,0] organophosphorus compound according to claim 1, characterized in that, Ar 1 It is a benzene ring, benzodioxane, or naphthalene ring; n is 0, 1, or 2; R 1 It is hydrogen, trifluoromethyl, C1-C3 alkoxy or C1-C3 saturated alkyl; R 2 It is a C1-C3 saturated alkyl, naphthyl, phenyl, or substituted phenyl; a substituted phenyl is a phenyl in which the hydrogen atom is replaced by a halogen atom or a C1-C3 saturated alkyl group; the halogen atom is chlorine or bromine.

3. A method for preparing the phosphorus heterobicyclic [3,2,0] organophosphorus compound according to claim 1, characterized in that, Includes the following steps: Step S1: ； Under inert gas protection, compound I was reacted with acetonitrile to obtain compound I-1 by adding a silanizing agent. The reaction was then carried out until completion, and the mixture was concentrated under reduced pressure to a dry state before being added to the next reaction step. Step S2: ； Under inert gas protection, compound I-1 was used as a raw material, dichloromethane was added as a solvent, and the mixture was cooled to 0°C. Under the catalysis of N,N-dimethylformamide, it was phosphonic with an acyl chloride reagent until the reaction was completed, to obtain phosphonic chloride compound I-2. Step S3: ； Under inert gas protection, the dried phosphonyl chloride compound I-2 was added to the dilute ether system, and Grignard reagent I-3 was added to phosphonyl chloride compound I-2 at 0°C. After the reaction was completed, the product was separated and purified to obtain dielyl organophosphorus compound II. Step S4: ； Under inert gas protection, the solvent was added to the reaction system containing dielyl organophosphorus compound II and Lawson's reagent, heated to reflux until the reaction was completed, concentrated under reduced pressure, and purified to obtain compound II-S1; Step S5: ； Under inert gas protection, the solvent was added to the reaction system containing dielyl organophosphorus compound II or II-S1, and then a photocatalyst was added. The photocatalyst was excited under a 390 nm light source to activate the double bond and realize the [2+2] cycloaddition reaction. After the reaction was completed, the target compound III was obtained by separation and purification.

4. The method for preparing the phosphorus heterobicyclic [3,2,0] organophosphorus compound according to claim 3, characterized in that, The photocatalyst in step S5 is selected from 10-phenylphenthiazide; the solvent in step S5 is selected from acetonitrile.

5. The application of the phosphatic bicyclic [3,2,0] organophosphorus compound of claim 1 in the Appel reaction, characterized in that, A phosphane-bicyclic [3,2,0] organophosphorus compound was used as a catalyst to catalyze the Appel reaction; the Appel reaction is a compound... As the reaction substrate, the catalyst was added, followed by the sequential addition of ultra-dry toluene, phenylsilane, and hexachloroacetone. The reaction system was sealed and reacted at 100°C for 24 hours to obtain... .

6. The application according to claim 5, characterized in that, The amount of catalyst used is 5 mol, based on the reaction substrate.

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