A trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphonooxide compound, its preparation method and application

Abstract

This invention discloses a trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphonooxide compound, its preparation method, and its applications. Using a diene-containing tertiary phosphonooxide compound as a starting material, a radical domino cyclization reaction is initiated with a trifluoromethyl reagent and a nucleophile, in the presence of a transition metal copper catalyst and a pyridine-oxazoline ligand, to obtain the compound. C-O, C-N, and C-C couplings are achieved, and the type of nucleophile can be changed to diversify the product structure. All diastereomers can be isolated, with a single diastereomer yield reaching 85%, exhibiting excellent diastereoselectivity. This invention provides a novel reaction mode for the radical-mediated construction of polysubstituted phosphatic six-membered rings, with mild reaction conditions, simple operation, and good substrate universality. It provides a novel skeletal structure for organophosphorus reagents and expands their diversity. The compound synthesized in this invention can be used as a catalyst in the Appel reaction, showing promising application prospects.

Description

Technical Field

[0001] This invention belongs to the field of catalysis technology, and relates to a trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphine oxide compound, its preparation method and application, and more specifically to a novel polysubstituted phosphatic six-membered ring organophosphine reagent as a catalyst for the Appel reaction. Background Technology

[0002] Organophosphorus reagents play a crucial role in organic synthesis. Organophosphorus compound-mediated Wittig, Staudinger, Appel, and Mitsunobu reactions are of great significance in scientific research and industrial production. Nucleophilic substitution of alcohols by halides plays a vital role in the synthesis of natural products and the formation of reactive intermediates. Traditional halogenation of alcohols typically uses highly reactive reagents, such as thionyl chloride or phosphorus trichloride [Appel, R]. Angew. Chem., Int. Ed. 1975, 14 [801.] This may lead to lower functional group compatibility and stereospecificity, or require prior activation of the alcohol, resulting in lower atom economy. The Appel reaction can use trivalent phosphine reagents and chlorides to form phosphonium chloride salts that react with alcohols, which can greatly improve stereospecificity to produce the corresponding haloalkanes. However, there is a major drawback: it requires a stoichiometric amount of trivalent phosphine reagent and produces a stoichiometric amount of phosphine oxide R3P=O byproduct, resulting in low atom economy [Longwitz L., Werner T., 801.]. Pure Appl. Chem. 2019, 91 [95–102.] This affects the post-processing and efficient separation of products. Therefore, a reducing agent is introduced into the reaction system to reduce P(V) to P(III), thereby achieving catalytic cycling, avoiding the generation of by-products, improving economic efficiency, and conforming to the concept of green chemistry [Pei MY; Li D.; Green Synthesis and Catalysis 2023, 4 [135–149.] Research on this catalytic mode has developed rapidly in recent years. In the P(Ⅲ) / P(Ⅴ) catalytic cycle, the reduction of P(Ⅴ) to P(Ⅲ) is a reverse thermodynamic process, and the reduction barrier of cyclic P(Ⅴ)=O is lower than that of acyclic P(Ⅴ)=O [Hérault, D., 135–149.]. Chem. Soc. Rev. 2015, 44, [2508.] Organophosphorus reagents with specially designed frameworks are favored by organic synthetic chemists [Kwon O.; Guo HC, Chem. Rev 2018, 118 [10049−10293.] However, research on phosphorus heterocycles used as catalysts for the Appel reaction mainly focuses on phosphorus heterocyclic five-membered rings and bridged phosphorus heterocyclic phosphine oxides [O'Brien CJ, ] Angew. Chem. Int. Ed.2014, 53 [12907–12911.], while phosphatic six-membered ring phosphonates are only used as examples in the screening conditions, and there are few reports on their research.

[0003] Phosphorus heterocyclic compounds are an important branch of organophosphorus compounds. Due to their unique structure and properties, they not only show broad application potential in coordination chemistry and catalysis, but also have significant development value in medicinal chemistry and materials science [Bruch A., Angew. Chem. Int. Ed., 2011, 50 [12094-12098.]. Currently, the main method for constructing functional phosphorus heterocyclic compounds is the reaction strategy using pre-prepared phosphorus-containing substrates and reactive metal reagents. This approach suffers from drawbacks such as demanding reaction conditions, poor atom economy, poor functional group tolerance, easy oxidation and instability of the substrate, numerous side reactions, low yields, and difficulty in large-scale preparation [Keller, PA, ]. J. Org. Chem. 2015, 80 [9774–9780.]. Therefore, exploring simple and efficient new methods for cyclization to construct phosphorus heterocyclic compounds has attracted the attention of organic synthetic chemists. In recent years, strategies for constructing phosphorus heterocycles from diene phosphine oxides have been commonly found in transition metal-catalyzed olefin metathesis reactions [Gouverneur, V., 9774–9780.]. Angew. Chem. Int. Ed. 2009, 48 [762–766.] or under superacid conditions, electrophilic substitution occurs to generate carbocations [Thibaudeau, S., ] Angew. Chem. Int. Ed. 2019, 58 [1355–1360.] However, the product skeleton structure is limited, constrained by the substrate itself. The construction of multi-substituted phosphata-six-membered rings via inexpensive transition metal-catalyzed radical domino cyclization reactions involving alkenyl tertiary phosphine oxides is rarely reported. Due to the high reactivity of radical intermediates and the complexity of the reaction process, using diene phosphine oxides as substrates allows for the efficient control of regioselectivity and stereoselectivity in the synthesis of phosphata-six-membered rings, while also suppressing radical coupling. β The competition from side reactions such as -H elimination, quenching, and hydrogen abstraction is quite challenging. The synthesis of nitrogen-containing and oxygen-containing heterocycles with quaternary carbon centers via radical domino cyclization has attracted considerable attention from scholars both domestically and internationally [Kiss L., Chem. Eur. J. 2023, 29 [e202203499.], but most of them terminated the reaction with free radicals without adding nucleophiles to build diverse skeletons, and this type of catalytic reaction has not been reported in the synthesis of phosphorus heterocyclic phosphine oxides. Summary of the Invention

[0004] Addressing the current state of phosphahexa-membered ring synthesis, this invention employs a three-component, inexpensive transition metal copper-catalyzed radical domino cyclization reaction to introduce a trifluoromethyl functional group into phosphine oxides. Simultaneously, it constructs multi-substituted phosphahexa-membered ring phosphine oxides containing a phosphine chiral center and two quaternary carbon chiral centers, achieving various coupling modes such as C–O, C–N, and C–C. This allows for modification of the nucleophile type, resulting in a diverse product structure. The synthesized phosphahexa-membered ring phosphine oxides are used as catalysts in the Appel reaction, providing novel skeletal structures for organophosphine reagents and expanding their diversity. The trifluoromethyl group, as a strong electron-withdrawing group, exhibits high chemical stability, metabolic stability, and significant lipophilicity. Introducing it into phosphahexa-membered ring molecules can regulate the lipophilic-hydrophilic balance of the entire molecule, making it easier to penetrate cell membranes and biological barriers, thus contributing to the development of novel drugs.

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

[0006] A polysubstituted phosphatic six-membered ring phosphonooxide containing trifluoromethyl groups, comprising any one of the following general structural formulas (1), (2), and (3):

[0007] In the general structural formula (1):

[0008] Ar 1 It is a benzene ring, benzo-1,3-dioxolane ring, or naphthalene ring; n is an integer, n is 0, 1, or 2;

[0009] R 1 It can be hydrogen, halogen atom, trifluoromethyl, C1~C6 saturated alkoxy or C1~C6 saturated alkyl;

[0010] R 2 It is a C1-C6 saturated alkyl, phenyl, or benzyl group; wherein the hydrogen atom on the phenyl or benzyl group may be replaced by a C1-C3 saturated alkyl or halogen atom.

[0011] R 3 It is hydrogen, C1~C6 saturated alkyl, C1~C6 cycloalkyl, benzyl, phenyl, , , , or ;

[0012] In the general structural formula (2):

[0013] Ar 1’ It is phenyl; R 1’ It is hydrogen or a C1~C3 saturated alkyl group; R 2’ It is phenyl;

[0014] R 4 For phenyl, substituted phenyl, , , or The hydrogen atom on a phenyl group can be replaced by a C1-C3 saturated alkyl or halogen atom.

[0015] In the general structural formula (3):

[0016] Ar 1” It is phenyl; R 1” It is hydrogen or a C1~C3 saturated alkyl group; R 2” It is phenyl;

[0017] R 5 for , , , , , , , or .

[0018] Preferably, in the general formula (1):

[0019] Ar 1 It is a benzene ring, benzo-1,3-dioxolane ring, or naphthalene ring; n is an integer, n is 0, 1, or 2;

[0020] R 1 It can be hydrogen, halogen atom, trifluoromethyl, C1~C3 saturated alkoxy or C1~C3 saturated alkyl;

[0021] R 2 It is a C1-C6 saturated alkyl, phenyl, or benzyl group; wherein the hydrogen atom on the phenyl or benzyl group may be replaced by a halogen atom; the halogen atom is bromine or chlorine;

[0022] R 3 It is hydrogen, C1~C3 saturated alkyl, cyclohexyl, benzyl, phenyl, , , , or ;

[0023] In the general structural formula (2):

[0024] Ar 1’ It is a benzene ring; R 1’ It is hydrogen or a C1~C3 saturated alkyl group; R 2’ It is phenyl;

[0025] R 4 For phenyl, substituted phenyl, , , or The substituted phenyl group is formed when the hydrogen atom on the phenyl group can be replaced by a C1-C3 saturated alkyl group or a halogen atom; the halogen atom is bromine or chlorine.

[0026] In the general structural formula (3):

[0027] Ar 1” It is phenyl; R 1” It is hydrogen or a C1~C3 saturated alkyl group; R 2” It is phenyl;

[0028] R 5 for , , , , , , , ,or .

[0029] The present invention also provides a method for preparing the above-mentioned compound, comprising the following steps:

[0030] Step S1:

[0031] Under inert gas protection, compound I was reacted with acetonitrile to obtain compound I-1, which was then reacted until the reaction was completed. The mixture was then concentrated under reduced pressure to a dry state before being added to the next reaction step.

[0032] Step S2:

[0033] Under inert gas protection, compound I-1 was used as a raw material, and dichloromethane was added as a solvent. The mixture was cooled to 0°C, and phosphonic was chlorinated with an acyl chloride reagent under the catalysis of N,N-dimethylformamide. The mixture was then transferred to room temperature and reacted until the reaction was completed. After the reaction was completed, the mixture was concentrated under reduced pressure to a dry state before being added to the next reaction step.

[0034] Step S3:

[0035] Under inert gas protection, dried phosphonyl chloride compound I-2 was added to an ether dilution system. Freshly prepared Grignard reagent I-3 was added to phosphonyl chloride compound I-2 at 0 °C, and the mixture was stirred overnight at room temperature. After extraction, the product was purified by column chromatography to obtain diene phosphonooxide compound II.

[0036] Step S4:

[0037] Under inert gas protection, an organic solvent was added to a reaction system using diene phosphine oxide II, oxygen nucleophiles III with different substituents, and trifluoromethyl reagent IV as raw materials. A copper metal precursor combined with a ligand was used as a catalyst. The mixture was stirred at 40–80 °C, followed by extraction, filtration, and vacuum concentration. The concentrated crude product was purified by column chromatography to obtain the target compound V, a six-membered phosphine oxide compound with oxygen as a nucleophile.

[0038] When the diene phosphine oxide II in the general structural formulas (1), (2), and (3) are the same, Ar 1 R 1 R 2 and R 3 same.

[0039] Step S5:

[0040] Under inert gas protection, an organic solvent was added to a reaction system using diene phosphine oxide II, nitrogen nucleophile VI with different substituents, and trifluoromethyl reagent IV as raw materials. A copper metal precursor combined with a ligand was used as a catalyst. The mixture was stirred at 40–80 °C, followed by extraction, filtration, and vacuum concentration. The concentrated crude product was purified by column chromatography to obtain the target compound VII, a phosphorus-containing six-membered ring phosphine oxide with nitrogen as the nucleophile.

[0041] Step S6:

[0042] Under inert gas protection, an organic solvent was added to a reaction system using diene phosphine oxide II, carbon nucleophiles VIII with different substituents, and trifluoromethyl reagent IV as raw materials. A copper metal precursor combined with a ligand was used as a catalyst. The mixture was stirred at 40–80 °C, followed by extraction, filtration, and vacuum concentration. The concentrated crude product was purified by column chromatography to obtain the target compound IX, a six-membered phosphine oxide compound with carbon as a nucleophile.

[0043] In this invention, the copper metal precursor (copper catalyst) mentioned in steps S4, S5 and S6 is selected from one of copper tetrafluoroborate tetraacetonitrile, copper hexafluorophosphate tetraacetonitrile, cuprous acetate, cuprous chloride, cuprous bromide, cuprous oxide, cuprous iodide, cuprous fluoride, cuprous sulfide, cuprous cyanide, cuprous acetylene, and cuprous nitrate.

[0044] In this invention, the ligands mentioned in steps S4, S5 and S6 are chiral nitrogen ligands, achiral nitrogen ligands, heterocyclic ligands (heterocyclic ligands), spirocyclic ligands, etc.

[0045] In this invention, the CF3 (trifluoromethyl) reagent mentioned in steps S4, S5, and S6 is selected from one of 3,3-dimethyl-1-(trifluoromethyl)-1,2-benzoiodopyrazine, 1-trifluoromethyl-1,2-benziodoyl-3(1H)-one, trifluoromethyltrimethylsilane, diphenyl(trifluoromethyl)sulfonium trifluoromethanesulfonate, S-(trifluoromethyl)dibenzothiophene tetrafluoroborate, S-(trifluoromethyl)dibenzothiophene trifluoromethanesulfonate, 5-(trifluoromethyl)-5H-dithiamone-5-trifluoromethanesulfonate, sodium trifluoromethylsulfinate, and trifluoroiodomethane.

[0046] In this invention, the organic solvents described in steps S4, S5, and S6 are one of the following or any mixture thereof: dichloromethane, dichloroethane, acetonitrile, propionitrile, butyronitrile, valerate, benzonitrile, phenylacetonitrile, diethyl ether, dibutyl ether, methyl tert-butyl ether, anisole, ethylene glycol dimethyl ether, ethyl acetate, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, xylene, benzene, chlorobenzene, fluorobenzene, trifluorotoluene, chloroform, and acetone.

[0047] In this invention, the feeding ratios in steps S4, S5, and S6 are as follows: the molar ratio between diene phosphine oxide II and nucleophiles with different substituents is 1:(1.0-2.0); the molar ratio between diene phosphine oxide II:copper metal precursor:ligand is 1:(0.03-0.2):(0.06-0.4); and the molar amount of diene phosphine oxide II to the volume ratio of organic solvent is 1 mmol:(1-10) mL.

[0048] As a preferred embodiment, in step S1, the molar ratio of the material of formula I and the silanizing agent is 1:4, the reaction temperature is 50 °C, and the reaction time is 2 hours.

[0049] 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.

[0050] 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.

[0051] In this invention, the molar ratio of diene phosphine oxide II, various types of nucleophiles, CF3 reagent, copper metal precursor, and ligand in steps S4, S5, and S6 is 1:5:1.5:0.1:0.11, the reaction temperature is 70 °C, the reaction time is 12 hours, and the mixture is concentrated under reduced pressure and then purified by column chromatography.

[0052] In this invention, the copper metal precursor in steps S4, S5 and S6 is selected from copper tetraacetonitrile tetrafluoroborate.

[0053] In this invention, the CF3 (trifluoromethyl) reagent in steps S4, S5 and S6 is selected from 3,3-dimethyl-1-(trifluoromethyl)-1,2-benzoiodopyrazine.

[0054] In this invention, the optimal ligand in steps S4, S5 and S6 is selected from (S)-4-tert-butyl-2-(2-pyridyl)oxazoline.

[0055] In this invention, the organic solvent in steps S4, S5 and S6 is selected from 1,2-dichloroethane.

[0056] This invention also protects the application of the trifluoromethyl-containing polysubstituted phosphorus six-membered ring phosphine oxide compound in catalysis; further, it protects its application in the in-situ generation of trivalent phosphine-catalyzed Appel reaction.

[0057] 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.

[0058] "Substitution" refers to the replacement of hydrogen atoms in a molecule by other different atoms or molecules.

[0059] The minimum and maximum carbon atom content in hydrocarbon groups are indicated by prefixes. For example, the prefixes Ca to Cb alkyl indicate any alkyl group containing "a" to "b" carbon atoms. Therefore, for example, C1 to C4 alkyl refers to alkyl groups containing 1 to 4 carbon atoms.

[0060] 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 C1-C6 alkoxy groups also have the corresponding meanings of their respective groups.

[0061] C1-C6 saturated alkyl groups refer to straight-chain or branched saturated alkyl groups (i.e., hydrocarbon groups containing only single bonds) consisting of 1 to 6 carbon atoms, without double or triple bonds. C1-C6 saturated alkoxy groups also have the corresponding meanings of their respective groups.

[0062] Compared with the prior art, the beneficial effects of the present invention are:

[0063] This invention provides a novel copper-catalyzed radical domino cyclization reaction for the synthesis of trifluoromethyl-containing, multi-substituted phosphata-six-membered ring phosphata-oxides from diene phosphata-oxides, achieving a single diastereomer yield of up to 85%, thus opening up new avenues for the synthesis of phosphata-six-membered ring phosphata-oxides. Through a three-component reaction, a trifluoromethyl functional group is introduced into the phosphata-oxide, simultaneously constructing three chiral centers. Multiple coupling reactions, including C–O, C–N, and C–C, are achieved by adding nucleophiles, allowing for variations in the nucleophile type and diversifying the product structure, significantly enriching the reaction strategy and the skeletal structure of phosphata-oxide products. The phosphata-six-membered ring phosphata-oxides provided by this invention, when used as catalysts in the Appel reaction, offer novel skeletal structures for organophosphine reagents and expand their diversity. Attached Figure Description

[0064] Figure 1 This is a route diagram for the synthesis of diene phosphine oxide II in Example 1 of the present invention;

[0065] Figure 2 This is the single-crystal diffraction structure of compound IX-2 of the present invention. Detailed Implementation

[0066] 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.

[0067] Example 1 Synthesis of diene phosphine oxide compound II:

[0068] 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. This 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 phosphonochlorinated with oxalyl 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. Compound I-2 was subjected to argon purging 3-5 times, and the reaction system was diluted with diethyl ether. The freshly prepared Grignard reagent I-3 was added at 0 °C, followed by stirring overnight at room temperature. After quenching the reaction, separation, filtration, drying, concentration under reduced pressure, and purification, diene phosphonooxide compound II was obtained. The synthetic steps are as follows: Figure 1 As shown (those skilled in the art can determine each R group based on the structural formulas of compounds I-1 to I-3, which will not be repeated here). The synthetic steps are described below:

[0069] Step S1: After purging with argon three times, trimethylbromosilane (40 mmol) was added to acetonitrile (10 mL) to starter 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.

[0070] 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.

[0071] Step S3: After purging with argon three times, compound I-2 was added to diethyl ether (10 mL) at 0 °C. The freshly prepared Grignard reagent (15 mmol) was then added to phosphonyl chloride compound I-2, 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 diene phosphonium oxides.

[0072] The characteristics of each diene phosphine oxide compound are as follows:

[0073] The characterization data of compound II-1 are as follows:

[0074]

[0075] 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 = 7.3,1.5 Hz, 1H), 7.29 – 7.20 (m, 12H), 5.37 (d, J = 4.5 Hz, 2H), 5.17 (d, J = 4.6Hz, 2H), 3.30 – 3.10 (m, 4H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 141.23 (d,J C-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.

[0076] The characterization data of compound II-2 are as follows:

[0077]

[0078] White solid (1.3 g, 34% yield). Melting point: 128.2–133.0 °C. 31 P{ 1 H} NMR (202MHz, 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 (126MHz, CDCl3) δ 141.00 (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 = 60.6 Hz). 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.

[0079] The characterization data of compound II-3 are as follows:

[0080]

[0081] White solid (2.0 g, 52% yield). Melting point: 135.0–156.5 °C. 31 P{ 1 H} NMR (162MHz, CDCl3) δ 33.76. 1 H NMR (400 MHz, CDCl3) δ 7.78 (ddd, J = 12.4, 7.5, 1.8Hz, 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 CNMR (100 MHz, CDCl3) δ 158.43 (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, JC-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.

[0082] The characterization data of compound II-4 are as follows:

[0083]

[0084] 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 C NMR (126 MHz, CDCl3) δ 139.42 (d, J C-P = 3.2 Hz), 137.95 (d, JC-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.

[0085] The characterization data of compound II-5 are as follows:

[0086]

[0087] 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, 1.6 Hz, 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 = 9.0Hz), 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 for C 28 H 26 OP + [M+H] + 409.1716, found 409.1722.

[0088] The characterization data of compound II-6 are as follows:

[0089]

[0090] 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 = 7.9,2.4 Hz, 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, JC-P = 8.7Hz), 132.10 (d, J C-P = 9.7 Hz), 128.33, 127.67, 126.36, 124.16 (d, J C-P = 99.0Hz), 117.83 (d, J C-P = 9.0 Hz), 110.52 (d, J C-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.

[0091] The characterization data of compound II-7 are as follows:

[0092]

[0093] 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 = 3.6Hz), 139.19 (d, J C-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 = 3.0 Hz). 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.

[0094] The characterization data of compound II-8 are as follows:

[0095]

[0096] 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)δ 7.55 (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 C NMR (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 = 2.5Hz), 131.46 (d, J C-P = 9.1 Hz), 128.29, 127.75, 126.23, 124.56(q, J C-F = 273.7Hz), 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 for C 25 H 23 F3OP + [M+H] + 427.1433, found 427.1439.

[0097] Example 2 Synthesis of polysubstituted phosphatic six-membered ring phosphonium oxide compound V with oxygen as a nucleophile

[0098] The reaction steps are as follows:

[0099] Specific experimental procedures: In a 10 mL sealed tube, add diene phosphine oxide compound II (0.2 mmol), copper tetraacetonitrile tetrafluoroborate (0.02 mmol), ligand (0.022 mmol), and 3,3-dimethyl-1-(trifluoromethyl)-1,2-benzoiodoxopentane (0.3 mmol) sequentially. The tube is purged five times under argon gas, and 1,2-dichloroethane (1 mL) and oxygen nucleophile (1 mmol) are added while maintaining purging. The reaction system is then sealed and the reaction is carried out at 70 °C for 12 hours. After the reaction is complete, the copper salt is removed by washing with sodium bicarbonate solution, dried, filtered, concentrated under reduced pressure, and purified by column chromatography using petroleum ether:ethyl acetate at a ratio of 4:1 to obtain compound V.

[0100] The characterization data of compound V-1 are as follows:

[0101]

[0102] Off-white solid (73.4 mg, 80% yield, dr 11.4 / 1). Melting point: 149.6–156.1 °C. 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 32.86. 19 F{ 1H} NMR (471 MHz, CDCl3) δ -58.62. 1 HNMR (500 MHz, CDCl3) δ 7.90 (ddd, J = 11.6, 7.7, 1.8 Hz, 2H), 7.71 – 7.67 (m,2H), 7.57 – 7.50 (m, 3H), 7.43 – 7.37 (m, 4H), 7.33 – 7.29 (m, 3H), 7.20 (t, J = 7.3 Hz, 1H), 3.10 (dq, J = 15.4, 10.6 Hz, 1H), 2.99 (d, J = 14.9 Hz, 1H),2.91 (ddd, J = 17.6, 15.2, 2.0 Hz, 1H), 2.81 – 2.69 (m, 2H), 2.63 (s, 3H),2.62 – 2.48 (m, 2H), 2.40 (dd, J = 15.4, 7.7 Hz, 1H). 13 C{ 1 H} NMR (126 MHz,CDCl3) δ 145.83 (d, J C-P = 12.7 Hz), 142.49 (d, J C-P = 4.9 Hz), 133.07 (d, J C-P =99.7 Hz), 132.05 (d, J C-P = 2.7 Hz), 130.65 (d, J C-P = 9.2 Hz), 128.80 (d, J C-P = 11.8 Hz), 128.59, 128.29, 128.08, 127.05, 126.78, 125.77 (q, J C-F = 279.4Hz), 125.57, 78.87, 49.97, 48.94 (d, J C-P = 8.4 Hz), 43.95 (q,J C-F = 25.9 Hz), 39.41, 38.08 (d, J C-P = 60.5 Hz), 35.01 (d, J C-P = 65.7 Hz). FT-IR (KBr): 3061,3035, 2992, 2944, 2915, 2820, 1497, 1448, 1437, 1426, 1405, 1383, 1323, 1255,1200, 1117, 1000, 969, 941, 913, 898, 872, 846, 832, 790, 769, 745, 702, 681,632, 593, 573, 542, 532, 517, 472, 439 cm -1 HRMS (ESI) calcd for C 26 H 27 F3O2P + [M+H] + 459.1695, found 459.1692.

[0103] The characterization data of compound V-2 are as follows:

[0104]

[0105] White solid (81.2 mg, 80% yield, dr 17.3 / 1). Melting point: 188.8–190.4 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 34.62. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ -58.25. 1 H NMR (500 MHz, CDCl3) δ 8.96 (d, J = 8.6 Hz, 1H), 8.12 – 8.05 (m, 2H), 7.96 (d, J = 8.2 Hz, 1H), 7.69 – 7.65 (m, 3H), 7.62 – 7.57 (m, 2H), 7.48 – 7.43 (m, 4H), 7.37 – 7.32 (m, 3H), 7.24 (dd, J= 7.1 Hz, 1H), 3.34 (dq, 1H), 3.08 – 2.99(m, 4H), 2.94 (d, J = 15.2 Hz, 1H), 2.84 (dd, J = 15.6, 7.0 Hz, 1H), 2.76(dq, J = 15.4, 10.7 Hz, 1H), 2.55 (s, 3H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ146.30 (d, J C-P = 12.6 Hz), 143.29 (d, J C-P = 6.6 Hz), 134.04 (d, J C-P = 9.1Hz), 133.44 (d, J C-P = 3.0 Hz), 133.23 (d, J C-P = 8.9 Hz), 131.34 (d, J C-P = 8.9Hz), 129.84, 129.49, 129.08, 128.61 (d, J C-P = 44.8 Hz), 127.97 (d, J C-P = 43.4Hz), 126.83, 126.78, 126.64, 126.03 (q, J C-F = 279.5 Hz), 125.98, 125.95,125.91, 124.76 (d, J C-P = 13.2 Hz), 79.36, 50.63, 47.83 (d, J C-P = 9.3 Hz),45.14 (q, J C-F = 25.5 Hz), 39.63, 38.65 (d, J C-P = 61.3 Hz), 33.52 (d, J C-P=65.8 Hz). FT-IR (KBr): 3058, 2972, 2924, 2828, 1595, 1497, 1447, 1386, 1324,1256, 1113, 988, 967, 941, 915, 895, 860, 823, 801, 774, 750, 701, 681, 633,592, 575, 550, 520, 490, 469, 436, 422 cm -1 HRMS (ESI) calcd for C 30 H 29 F3O2P + [M+H] + 509.1852, found 509.1852.

[0106] The characterization data for compound V-3 are as follows:

[0107]

[0108] Colorless oil (75.7 mg, 75% yield, dr 11.6 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.49. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.61. 1 H NMR (400 MHz, CDCl3)δ 7.68 – 7.64 (m, 2H), 7.47 – 7.39 (m, 5H), 7.36 – 7.31 (m, 3H), 7.29 (dd, J = 10.9, 1.5 Hz, 1H), 7.27 – 7.19 (m, 1H), 6.97 (dd, J = 7.9, 2.4 Hz, 1H), 6.05 (s, 2H), 3.07 (dq, J = 15.5, 10.6 Hz, 1H), 2.96 (d, J = 14.9 Hz, 1H), 2.87 (ddd, J = 17.6, 15.3, 2.0 Hz, 1H), 2.78 – 2.68 (m, 2H), 2.64 (s, 3H), 2.61 – 2.44 (m, 2H), 2.37 (ddd,J = 15.4, 7.8, 1.2 Hz, 1H). 13 C{ 1 H} NMR (100MHz, CDCl3) δ 151.08 (d, J C-P = 3.0 Hz), 148.39 (d, J C-P = 17.9 Hz), 146.03 (d, J C-P = 12.8 Hz), 142.71 (d, J C-P = 5.4 Hz), 128.76, 128.44, 128.22, 127.12, 126.93, 126.29 (d, J C-P = 10.1 Hz), 126.23 (d, J C-P = 103.4 Hz), 125.87 (q, J C-F = 279.4 Hz), 125.76, 110.19 (d, J C-P = 12.3 Hz), 109.04 (d, J C-P = 14.7 Hz),101.86, 79.07 (d, J C-P = 1.4 Hz), 50.24, 48.69 (d, J C-P = 8.4 Hz), 44.29 (q, J C-F = 25.9 Hz), 39.53 (dd, J C-F = 3.1, J C-P = 1.8 Hz), 38.82 (d, J C-P = 60.9Hz), 35.42 (d, J C-P= 66.1 Hz). FT-IR (KBr): 3067, 2986, 2934, 2918, 1508,1447, 1428, 1385, 1322, 1249, 1192, 1123, 1067, 1036, 970, 933, 900, 847,834, 814, 788, 768, 731, 714, 698, 681, 644, 636, 601, 574, 539, 506, 418 cm -1 HRMS (ESI) calcd for C 27 H 27 F3O4P + [M+H] + 503.1594, found 503.1593.

[0109] The characterization data of compound V-4 are as follows:

[0110]

[0111] Colorless oil (76.2 mg, 81% yield, dr 9.3 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 39.71. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.48. 1 H NMR (500 MHz, CDCl3) δ 7.57– 7.52 (m, 2H), 7.42 – 7.38 (m, 3H), 7.36 (td, J = 5.5, 4.8, 2.1 Hz, 7H),7.33 – 7.29 (m, 2H), 7.26 – 7.23 (m, 1H), 3.37 – 3.25 (m, 2H), 2.82 (dq, J =15.5, 10.7 Hz, 1H), 2.71 – 2.62 (m, 2H), 2.61 (s, 3H), 2.59 – 2.40 (m, 4H), 2.23 (dd, J = 15.1, 8.5 Hz, 1H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 145.26 (d, JC-P = 10.3 Hz), 142.73 (d, J C-P = 6.0 Hz), 131.57 (d, J C-P = 8.1 Hz), 129.90 (d, J C-P = 5.4 Hz), 129.03 (d, J C-P = 2.5 Hz), 128.76, 128.37, 128.18, 127.31 (d, J C-P = 3.1 Hz), 126.90, 126.85, 125.86, 125.75 (d, J C-F = 279.4 Hz), 79.23,50.13, 48.73 (d, J C-P = 7.3 Hz), 45.53 (q, J C-F = 26.5 Hz), 39.90 (d, J C-P =63.8 Hz), 39.69, 34.38 (d, J C-P = 59.1 Hz), 33.63 (d, J C-P = 62.4 Hz). FT-IR(KBr): 3061, 3031, 2943, 2826, 1497, 1447, 1407, 1381, 1327, 1262, 1200,1157, 1120, 1067, 1002, 968, 942, 911, 855, 825, 768, 731, 699, 643, 590,573, 492 cm -1 HRMS (ESI) calcd for C 27 H 29 F3O2P + [M+H] + 473.1852, found 473.1852.

[0112] The characterization data for compound V-5 are as follows:

[0113]

[0114] Colorless oil (66.2 mg, 68% yield, dr 10.4 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 32,88. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.38. 1 H NMR (500 MHz, CDCl3)δ 7.90 (dd, J = 10.5, 7.2 Hz, 2H), 7.61 – 7.53 (m, 5H), 7.29 (d, J = 8.1 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 7.9 Hz, 2H), 3.06 (dq, J = 15.3, 10.7 Hz, 1H), 2.97 (d, J = 14.4 Hz, 1H), 2.91 (d, J = 17.4 Hz, 1H), 2.76 (t, J = 15.7 Hz, 1H), 2.70 – 2.64 (m, 4H), 2.57 – 2.48 (m, 2H), 2.42 – 2.34 (m,4H), 2.31 (s, 3H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 143.10 (d, J C-P = 12.8 Hz), 139.51 (d, J C-P = 4.8 Hz), 137.90, 136.40, 133.37 (d, J C-P = 99.3 Hz), 132.07(d, J C-P = 2.8 Hz), 130.79 (d, J C-P = 9.5 Hz), 129.36, 129.05, 128.86 (d, J C-P=11.7 Hz), 127.15, 125.94 (q, J C-F = 279.5 Hz), 125.55, 78.89, 49.96, 49.19 (d, J C-P = 8.0 Hz), 44.04 (q, J C-F = 25.8 Hz), 39.26, 38.09 (d, J C-P = 60.5 Hz), 35.48 (d, J C-P = 65.5 Hz), 21.10, 20.91. FT-IR (KBr): 3057, 3026, 2942, 2826,1515, 1438, 1381, 1319, 1262, 1194, 1116, 1069, 1020, 969, 930, 909, 849,817, 735, 695, 674, 644, 581, 547, 538, 501, 474 cm -1 HRMS (ESI) calcd for C 28 H 31 F3O2P + [M+H] + 487.2008, found 487.2007.

[0115] The characterization data for compound V-6 are as follows:

[0116]

[0117] Colorless oil (77.7 mg, 74% yield, dr 11.2 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 31.56. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.45. 1 H NMR (400 MHz, CDCl3)δ 7.86 (ddd, J= 11.7, 7.9, 1.6 Hz, 2H), 7.65 – 7.61 (m, 2H), 7.61 – 7.50 (m,3H), 7.42 – 7.38 (m, 2H), 7.34 – 7.28 (m, 4H), 3.04 (dq, J = 15.5, 10.6 Hz,1H), 2.89 (ddd, J = 17.7, 15.2, 2.0 Hz, 2H), 2.77 – 2.70 (m, 1H), 2.68 (s,3H), 2.63 (d, J = 14.9 Hz, 1H), 2.59 – 2.44 (m, 2H), 2.37 (dd, J = 15.4, 7.8Hz, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 144.35 (d, J C-P = 12.6 Hz), 141.05 (d, J C-P = 4.6 Hz), 134.28, 132.87, 132.63 (d, J C-P = 100.2 Hz), 132.38 (d, J C-P =2.8 Hz), 130.70 (d, J C-P = 9.4 Hz), 129.01 (d, J C-P = 11.9 Hz), 128.94, 128.80,128.57, 127.16, 125.66 (q, J C-F = 279.5 Hz), 78.72 (d, J C-P = 1.5 Hz), 50.08,49.10 (d, J C-P = 8.4 Hz), 43.98 (q, J C-F = 25.8 Hz), 39.42 (dd, J C-F = 3.0, J C-P= 1.6 Hz), 37.56 (d, J C-P = 60.5 Hz), 35.42 (d, J C-P = 65.3 Hz). FT-IR (KBr):3058, 2941, 2827, 1593, 1574, 1494, 1438, 1381, 1311, 1260, 1114, 1012, 969,948, 934, 906, 824, 779, 741, 695, 663, 644, 634, 592, 578, 566, 527, 492,473, 459 cm -1 HRMS (ESI) calcd for C 26 H 25 Cl2F3O2P + [M+H] + 527.0916, found 527.0915.

[0118] The characterization data for compound V-7 are as follows:

[0119]

[0120] Yellow oily substance (85.3 mg, 81% yield, dr 11.7 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 32.58. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.54, –63.02. 1 H NMR (500 MHz, CDCl3) δ 8.06 (dd, J = 11.1, 8.0 Hz, 2H), 7.82 (dd, J = 8.3, 2.3 Hz, 2H),7.66 – 7.61 (m, 2H), 7.47 – 7.39 (m, 4H), 7.37 – 7.32 (m, 3H), 7.24 (t, J =7.4 Hz, 1H), 3.12 (dq, J = 15.4, 10.5 Hz, 1H), 2.98 (d, J= 15.0 Hz, 1H),2.93 – 2.76 (m, 3H), 2.68 (dd, J = 15.3, 7.4 Hz, 1H), 2.63 (s, 3H), 2.62 –2.54 (m, 1H), 2.46 (ddd, J = 15.5, 7.6, 1.4 Hz, 1H). 13 C{ 1 H} NMR (126 MHz,CDCl3) δ 145.79 (d, J C-P = 12.8 Hz), 142.59 (d, J C-P = 6.0 Hz), 137.80 (d, J C-P = 96.1 Hz), 134.04 (qd, J C-F = 32.5, J C-P = 2.5 Hz), 131.52 (d, J C-P = 9.6 Hz),128.98, 128.55, 128.37, 127.08, 126.88, 126.08 (q, J C-P = 279.5 Hz), 125.82(d, J C-P = 3.7 Hz), 125.71, 123.88 (q, J C-F = 273.12 Hz) 78.90, 50.47, 48.29(d, J C-P = 8.5 Hz), 44.72 (q, J C-F = 25.8 Hz), 39.50, 39.05 (d, J C-P = 60.9 Hz),34.67 (d, J C-P= 66.1 Hz). FT-IR (KBr): 3062, 3037, 2937, 1736, 1498, 1448,1399, 1325, 1263, 1124, 1018, 969, 944, 912, 897, 829, 789, 769, 746, 701,680, 595, 575, 552, 525, 504, 420 cm -1 HRMS (ESI) calcd for C 27 H 26 F6O2P + [M+H] + 527.1569, found 527.1568.

[0121] The characterization data for compound V-8 are as follows:

[0122]

[0123] White solid (65.2 mg, 67% yield, dr 8.8 / 1). Melting point: 187.8–189.2 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 31.56. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.61. 1 H NMR (500 MHz, CDCl3) δ 8.15 (ddd, J = 13.3, 7.5, 1.8 Hz, 1H), 7.87 (d, 2H), 7.59(ddt, J = 8.7, 6.8, 1.6 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.39 – 7.31 (m,5H), 7.25 – 7.19 (m, 2H), 6.98 (dd, J = 8.3, 5.4 Hz, 1H), 3.89 (s, 3H), 3.11(dt, J = 14.4, 1.9 Hz, 1H), 3.01 (ddt, J = 17.2, 15.0, 2.1 Hz, 1H), 2.89 (dq,1H), 2.82 (dd, J= 14.7, 8.6 Hz, 1H), 2.78 (s, 3H), 2.71 (dd, J = 14.9, 10.7Hz, 1H), 2.64 (ddt, J = 16.9, 14.4, 2.7 Hz, 1H), 2.41 (d, J = 14.4 Hz, 1H),2.22 (dq, J = 15.6, 10.8 Hz, 1H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 159.42 (d, J C-P = 4.2 Hz), 146.13 (d, J C-P = 13.9 Hz), 142.19, 135.35 (d, J C-P = 5.9 Hz),134.54 (d, J C-P = 2.2 Hz), 128.51, 128.33, 128.22, 128.21, 126.79, 125.96 (q, J C-F = 279.5 Hz), 125.56, 121.52 (d, J C-P = 10.9 Hz), 119.54 (d, J C-P = 97.8Hz), 110.91 (d, J C-P = 6.8 Hz), 79.23, 55.66, 51.58 (d, J C-P = 7.2 Hz), 49.07,42.27 (q, J C-F = 25.9 Hz), 39.69, 34.13 (d, J C-P= 123.5 Hz), 34.12. FT-IR(KBr): 3066, 3026, 2989, 2947, 2826, 1591, 1578, 1497, 1479, 1410, 1381,1321, 1259, 1196, 1069, 1016, 968, 944, 910, 871, 847, 801, 789, 762, 693,632, 591, 571, 540, 519, 484, 432 cm -1 HRMS (ESI) calcd for C 27 H 29 F3O3P + [M+H] + 489.1801, found 489.1800.

[0124] The characterization data for compound V-9 are as follows:

[0125]

[0126] Colorless oil (86.9 mg, 74% yield, dr 11.1 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 34.85. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ -58.42. 1 H NMR (400 MHz, CDCl3)δ 8.50 – 8.43 (m, 1H), 8.30 (dd, J = 10.8, 8.5 Hz, 1H), 8.02 (d, 1H), 7.90(dd, J = 6.9, 2.7 Hz, 1H), 7.81 (d, 2H), 7.71 – 7.62 (m, 2H), 7.47 (t, J =7.7 Hz, 2H), 7.43 (d, J = 7.7 Hz, 2H), 7.38 – 7.32 (m, 3H), 7.24 (dd, 1H), 3.46 (dd, J = 14.6, 7.8 Hz, 1H), 3.23 (dd, J= 15.3, 9.4 Hz, 1H), 3.18 – 3.04(m, 3H), 2.86 (dd, 1H), 2.76 – 2.67 (m, 4H), 2.40 (dq, J = 15.3, 10.8 Hz,1H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 145.95 (d, J C-P = 13.5 Hz), 142.58 (d, J C-P = 3.4 Hz), 136.24 (d, J C-P = 2.2 Hz), 132.56 (d, J C-P = 9.1 Hz), 130.70 (d, J C-P = 96.6 Hz), 129.34 (d, J C-P = 7.7 Hz), 128.99, 128.67, 128.51, 128.44, 128.41,128.29, 127.89, 127.64, 127.00 (d, J C-P = 4.9 Hz), 126.93, 126.14 (d, J C-P =20.8 Hz), 125.94 (q, J C-F = 279.68 Hz), 125.64, 79.37, 50.24 (d, J C-P = 8.7Hz), 49.64, 43.20 (q, J C-F = 26.1 Hz), 39.85 (t, J C-P = 2.2 Hz), 34.72 (d, J C-P = 62.0 Hz), 32.93 (d, J C-P= 67.5 Hz). FT-IR (KBr): 3059, 2933, 2825, 1548,1497, 1447, 1381, 1313, 1261, 1216, 1191, 1153, 1138, 1120, 1083, 1068, 968,944, 910, 895, 866, 822, 789, 770, 744, 732, 713, 699, 680, 670, 641, 610,588, 572, 534, 513, 444, 419 cm -1 HRMS (ESI) calcd for C 30 H 28 BrF3O2P + [M+H] + 587.0957, found 587.0955.

[0127] The characterization data for compound V-10 are as follows:

[0128]

[0129] White solid (67.8 mg, 72% yield, dr 10.8 / 1). Melting point: 167.3–170.2 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 34.27. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.43. 1 H NMR (400 MHz, CDCl3) δ 7.70 (dd, J = 12.6, 7.8 Hz, 1H), 7.62 (d, J = 7.3 Hz, 2H),7.50 – 7.38 (m, 5H), 7.40 – 7.29 (m, 5H), 7.26 – 7.21 (m, 1H), 3.24 (dq, J =15.5, 10.7 Hz, 1H), 3.01 – 2.81 (m, 4H), 2.81 (s, 4H), 2.75 – 2.61 (m, 1H), 2.60 (dd, J = 15.0, 6.8 Hz, 1H), 2.54 (s, 3H). 13 C{1 H} NMR (100 MHz, CDCl3) δ146.36 (d, J C-P = 12.5 Hz), 143.28 (d, J C-P = 6.2 Hz), 142.31 (d, J C-P = 8.2Hz), 132.44 (d, J C-P = 10.7 Hz), 132.12, 132.10, 131.13, 130.58 (d, J C-P = 10.7Hz), 128.78, 128.44, 128.11, 126.84, 126.05, 126.03 (q, J C-F = 279.5 Hz),125.91 (d, J C-P = 3.6 Hz), 79.23 (d, J C-P = 1.7 Hz), 50.46, 48.16 (d, J C-P = 9.0Hz), 44.82 (q, J C-F = 25.9 Hz), 39.56 (dd, J C-F = 3.0, J C-F = 1.8 Hz), 38.15 (d, J C-P = 61.0 Hz), 33.09 (d, J C-P = 65.9 Hz), 21.74 (d, J C-P = 3.6 Hz). FT-IR(KBr): 3061, 2949, 2923, 2825, 1498, 1402, 1379, 1310, 1256, 1188, 1087,1033, 968, 939, 917, 897, 869, 804, 786, 753, 734, 719, 700, 686, 575, 558,485, 469, 443, 434, 413 cm -1HRMS (ESI) calcd for C 27 H 29 F3O2P + [M+H] + 473.1852, found 473.1851.

[0130] The characterization data of compound V-11 are as follows:

[0131]

[0132] White solid (66 mg, 74% yield, dr 13.2 / 1). Melting point: 132.1–134.9 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 33.70. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.78. 1 H NMR (400 MHz, CDCl3) δ 7.82 (dd, J = 11.7, 7.5 Hz, 2H), 7.58 (d, J = 7.7 Hz, 2H), 7.53 (d, J = 7.1 Hz, 1H), 7.47 (td, J = 7.6, 2.6 Hz, 2H), 7.42 – 7.35 (m,4H), 7.34 – 7.28 (m, 3H), 7.23 (t, J = 7.2 Hz, 1H), 3.09 – 2.80 (m, 5H), 2.75(s, 1H), 2.62 (d, J = 16.3 Hz, 1H), 2.58 – 2.40 (m, 2H). 13 C NMR (100 MHz, CDCl3) δ 148.78 (d, J C-P = 9.7 Hz), 146.53 (d, J C-P = 11.4 Hz), 133.21 (d, J C-P = 98.2 Hz), 132.06 (d, J C-P = 2.9 Hz), 130.81 (d,J C-P = 9.7 Hz), 128.81, 128.79 (d, J C-P = 12.0 Hz), 128.77, 127.70, 126.95, 125.89 (q, J C-F = 279.1Hz), 125.80, 124.55, 74.04 (d, J C-P = 2.1 Hz), 47.92 (q, J C-F = 25.9 Hz), 45.10(d, J C-P = 11.6 Hz), 43.91 (d, J C-P = 61.3 Hz), 39.34 (d, J C-P = 1.9 Hz), 36.73(d, J C-P = 63.5 Hz). FT-IR (KBr): 3166, 3061, 3027, 2970, 2948, 2927, 1495,1446, 1438, 1376, 1346, 1311, 1261, 1185, 1141, 1121, 1062, 1035, 1000, 968,881, 827, 797, 773, 750, 736, 699, 682, 592, 572, 532, 511, 485, 467 cm -1 .HRMS (ESI) calcd for C 25 H 25 F3O2P + [M+H] + 445.1539, found 445.1539.

[0133] The characterization data for compound V-12 are as follows:

[0134]

[0135] Colorless oil (68.9 mg, 73% yield, dr 10.7 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.27.19 F{ 1 H} NMR (376 MHz, CDCl3) δ -58.60. 1 H NMR (400 MHz, CDCl3)δ 7.91 (ddd, J = 11.6, 7.7, 1.8 Hz, 2H), 7.75 – 7.68 (m, 2H), 7.64 – 7.50 (m,3H), 7.47 – 7.38 (m, 4H), 7.33 (t, J = 7.7 Hz, 3H), 7.23 (t, J = 7.2 Hz, 1H),3.14 – 2.88 (m, 4H), 2.84 – 2.69 (m, 2H), 2.69 – 2.46 (m, 3H), 2.44 (dd, J =15.5, 7.8 Hz, 1H), 0.88 (t, J = 6.9 Hz, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ145.96 (d, J C-P = 12.7 Hz), 143.26 (d, J C-P = 4.8 Hz), 133.34 (d, J C-P = 99.5Hz), 132.17 (d, J C-P = 2.9 Hz), 130.82 (d, J C-P = 9.4 Hz), 128.93 (d, J C-P =11.8 Hz), 128.69, 128.37, 128.15, 127.10, 126.92, 125.89 (q, J C-F = 279.3 Hz),125.72, 78.56 (d, J C-P = 1.7 Hz), 57.52, 49.57 (d, J C-P = 8.2 Hz), 44.11 (q, J C-F= 25.8 Hz), 39.63 (dd, J C-P = 3.3, 1.8 Hz), 38.59 (d, J C-P = 60.2 Hz), 35.43 (d, J C-P = 65.7 Hz), 15.20. FT-IR (KBr): 3059, 3033, 2974, 2927, 1498,1447, 1439, 1383, 1310, 1261, 1189, 1169, 1140, 1120, 1085, 1066, 962, 911,843, 747, 716, 698, 680, 644, 590, 518, 487, 434 cm -1 HRMS (ESI) calcd for C 27 H 29 F3O2P + [M+H] + 473.1852, found 473.1851.

[0136] The characterization data for compound V-13 are as follows:

[0137]

[0138] Yellow oily substance (57.8 mg, 56% yield, dr 10.5 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.40. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.68. 1 H NMR (400 MHz, CDCl3)δ 7.66 (d, J = 7.7 Hz, 2H), 7.50 – 7.43 (m, 6H), 7.42 – 7.32 (m, 6H), 7.26(t, 1H), 7.00 (t, J = 7.8 Hz, 2H), 6.82 (t, J = 7.3 Hz, 1H), 6.24 (d, J = 8.1Hz, 2H), 3.19 (d, J= 15.4 Hz, 1H), 3.07 (t, J = 17.4 Hz, 1H), 3.00 – 2.86(m, 4H), 2.73 (t, J = 15.8 Hz, 1H), 2.61 (dd, J = 14.9, 6.7 Hz, 1H). 13 C{ 1 H}NMR (100 MHz, CDCl3) δ 153.93, 145.96 (d, J C-P = 11.4 Hz), 144.37 (d, J C-P = 6.7Hz), 132.64 (d, J C-P = 101.9 Hz), 132.16, 130.49 (d, J C-P = 9.6 Hz), 129.27,129.11, 128.84 (d, J C-P = 11.8 Hz), 128.21, 128.10, 126.68, 126.06, 125.96,125.89 (q, J C-F = 279.4 Hz), 121.57, 118.71, 81.52, 49.22 (d, J C-P = 12.2 Hz),46.92 (q, J C-F = 25.7 Hz), 39.74 (dd, J C-P = 3.4, 1.8 Hz), 36.59 (d, J C-P = 64.7Hz), 35.44 (d, J C-P= 62.9 Hz). FT-IR (KBr): 3060, 3035, 1597, 1489, 1447,1438, 1377, 1262, 1186, 1117, 1084, 1032, 1000, 974, 909, 877, 863, 836, 787,733, 696, 644, 617, 605, 590, 548, 526, 493 cm -1 HRMS (ESI) calcd for C 31 H 29 F3O2P + [M+H] + 521.1852, found 521.1854.

[0139] The characterization data for compound V-14 are as follows:

[0140]

[0141] Colorless oil (76.7 mg, 72% yield, dr 10.2 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.22. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.61. 1 H NMR (400 MHz, CDCl3)δ 7.88 – 7.74 (m, 4H), 7.59 – 7.52 (m, 1H), 7.52 – 7.40 (m, 6H), 7.39 – 7.31(m, 3H), 7.28 – 7.18 (m, 4H), 6.95 (dd, J = 6.7, 2.9 Hz, 2H), 4.03 (d, J =11.2 Hz, 1H), 3.77 (d, J = 11.2 Hz, 1H), 3.13 – 2.98 (m, 3H), 2.90 (d, J =15.1 Hz, 1H), 2.77 (dd, 1H), 2.67 – 2.50 (m, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl3)δ 145.99 (d, JC-P = 12.5 Hz), 142.88 (d, J C-P = 5.2 Hz), 138.09, 133.12 (d, J C-P = 99.6 Hz), 132.15 (d, J C-P = 2.9 Hz), 130.75 (d, J C-P = 9.3 Hz), 128.91 (d, J C-P = 11.8 Hz), 128.88, 128.45, 128.40, 128.33, 127.44, 127.21, 127.16,126.91, 125.88 (q, J C-F = 279.4 Hz), 125.81, 79.45 (d, J C-P = 1.6 Hz), 64.41,49.51 (d, J C-P = 9.0 Hz), 44.67 (q, J C-F = 25.7 Hz), 39.63 (dd, J C-P = 3.3, 1.8Hz), 37.89 (d, J C-P = 60.7 Hz), 35.49 (d, J C-P = 65.6 Hz). FT-IR (KBr): 3060,3031, 2917, 2866, 1497, 1447, 1438, 1381, 1310, 1261, 1198, 1120, 1085, 1060,1036, 1000, 969, 911, 833, 779, 735, 716, 697, 645, 591, 513, 482 cm -1 . HRMS(ESI) calcd for C 32 H 31 F3O2P + [M+H] + 535.2008, found 535.2009.

[0142] The characterization data for compound V-15 are as follows:

[0143]

[0144] Colorless oil (67.2 mg, 70% yield, dr 11.5 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 30.85. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.66. 1 H NMR (500 MHz, CDCl3)δ 7.95 – 7.87 (m, 4H), 7.62 – 7.56 (m, 3H), 7.47 (t, J = 7.6 Hz, 2H), 7.40 –7.30 (m, 5H), 7.23 (t, J = 7.0 Hz, 1H), 3.44 (hept, J = 6.2 Hz, 1H), 3.29 (t, J = 15.7 Hz, 1H), 3.20 (dt, J = 14.6, 2.2 Hz, 1H), 2.86 – 2.72 (m, 2H), 2.27(ddd, J = 28.4, 14.5, 6.2 Hz, 3H), 2.11 (dq, J = 15.7, 10.7 Hz, 1H), 1.00 (d, J = 6.1 Hz, 3H), 0.76 (d, J = 6.1 Hz, 3H). 13 C{ 1 H} NMR (126 MHz, CDCl3) 145.53(d, J C-P = 12.7 Hz), 141.71, 133.00 (d, J C-P = 99.9 Hz), 132.27 (d, J C-P = 3.0Hz), 130.82 (d, J C-P = 8.9 Hz), 129.04 (d,J C-P = 11.5 Hz), 128.64, 128.55,128.39, 128.23, 127.04, 125.92 (q, J C-F =279.34 Hz), 125.49, 79.12, 64.89,53.28 (d, J C-P = 5.7 Hz), 41.57 (q, J C-F = 26.4 Hz), 40.25, 37.29 (d, J C-P =58.1 Hz), 36.29 (d, J C-P = 66.0 Hz), 25.38, 24.21. FT-IR (KBr): 3060, 3035,2973, 2929, 1498, 1447, 1438, 1382, 1321, 1261, 1197, 1161, 1139, 1118, 1018,965, 931, 911, 897, 856, 839, 787, 774, 749, 716, 697, 680, 644, 584, 545,523, 506 cm -1 HRMS (ESI) calcd for C 28 H 31 F3O2P + [M+H] + 487.2008, found487.2008.

[0145] The characterization data for compound V-16 are as follows:

[0146]

[0147] Yellow oily substance (81.0 mg, 77% yield, dr 11.2 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 30.92. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.64. 1 H NMR (400 MHz, CDCl3)δ 7.91 (dd, J= 8.9 Hz, 4H), 7.63 – 7.53 (m, 3H), 7.45 (t, J = 7.6 Hz, 2H),7.40 – 7.29 (m, 5H), 7.24 (dd, J = 12.8, 5.8 Hz, 1H), 3.26 (t, J = 16.0 Hz,1H), 3.18 (d, J = 14.8 Hz, 1H), 3.12 – 3.03 (m, 1H), 2.89 – 2.73 (m, 2H),2.37 (d, J = 14.6 Hz, 1H), 2.34 – 2.24 (m, 2H), 2.14 (dq, J = 15.5, 10.8 Hz,1H), 2.07 – 1.91 (m, 1H), 1.63 – 1.50 (m, 2H), 1.49 – 1.41 (m, 1H), 1.40 –1.29 (m, 1H), 1.29 – 1.13 (m, 2H), 1.10 – 0.94 (m, 3H), 0.94 – 0.78 (m, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 145.68 (d, J C-P = 12.7 Hz), 142.10, 133.15 (d, J C-P = 99.8 Hz), 132.23 (d, J C-P = 2.9 Hz), 130.83 (d, J C-P = 8.9 Hz), 129.03(d, J C-P = 11.7 Hz), 128.49, 128.39, 128.17, 127.01, 125.95 (q, J C-F = 279.5Hz), 125.54, 78.96, 70.98, 53.03 (d, J C-P = 6.1 Hz), 41.92 (q, J C-F= 26.5 Hz), 40.04, 37.57 (d, J C-P = 58.3 Hz), 36.16 (d, J C-P = 66.2 Hz), 34.90 (d, J C-P =157.5 Hz), 25.44, 24.51 (d, J C-P = 7.9 Hz). FT-IR (KBr): 2932, 2855, 1498,1447, 1438, 1382, 1309, 1261, 1198, 1167, 1139, 1120, 1037, 966, 942, 911,895, 843, 780, 751, 715, 698, 602, 588, 518, 493 cm -1 HRMS (ESI) calcd for C 31 H 35 F3O2P + [M+H] + 527.2321, found 527.2322.

[0148] The characterization data for compound V-17 are as follows:

[0149]

[0150] Yellow oily substance (73.7 mg, 66% yield, dr 12 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 31.58. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.60. 1 H NMR (500 MHz, CDCl3) δ 7.91(dd, 2H), 7.81 (d, J = 7.8 Hz, 2H), 7.59 – 7.54 (m, 1H), 7.51 (td, J = 7.5, 2.3 Hz, 2H), 7.46 (t, J = 7.7 Hz, 2H), 7.38 (t, J= 8.2 Hz, 3H), 7.35 – 7.27(m, 4H), 7.27 – 7.20 (m, 4H), 3.81 (d, J = 15.2 Hz, 1H), 3.62 (d, J = 15.2Hz, 1H), 3.16 – 3.06 (m, 2H), 2.99 (dq, J = 15.5, 10.6 Hz, 1H), 2.80 (t, J =15.8 Hz, 1H), 2.68 (d, J = 14.9 Hz, 1H), 2.56 (dd, J = 13.3, 6.2 Hz, 1H),2.54 – 2.49 (m, 1H), 2.41 (dq, J = 15.4, 10.6 Hz, 1H). 13 C{ 1 H} NMR (100 MHz,CDCl3) δ 145.56 (d, J C-P = 12.7 Hz), 141.67 (d, J C-P = 3.5 Hz), 132.90 (d, J C-P = 100.3 Hz), 132.27 (d, J C-P = 2.9 Hz), 131.70, 130.88 (d, J C-P = 9.2 Hz),128.97 (d, J C-P = 11.8 Hz), 128.94, 128.73, 128.54, 128.49, 128.34, 127.62,127.06, 125.84 (q, J C-F = 279.4 Hz), 125.63, 122.62, 85.78, 85.61, 80.17 (d, J C-P = 1.4 Hz), 51.70, 50.32 (d, J C-P = 7.7 Hz), 43.30 (q, J C-F= 26.0 Hz), 39.78 (dd, J C-P = 3.2, 1.7 Hz), 37.98 (d, J C-P = 59.6 Hz), 35.67 (d, J C-P = 65.4Hz). FT-IR (KBr): 3059, 2932, 2855, 2230, 1498, 1447, 1438, 1382, 1309, 1261,1198, 1167, 1139, 1120, 1037, 966, 942, 911, 843, 780, 751, 715, 698, 643,602, 588, 518 cm -1 HRMS (ESI) calcd for C 34 H 31 F3O2P + [M+H] + 559.2008, found559.2007.

[0151] The characterization data for compound V-18 are as follows:

[0152]

[0153] Yellow oily substance (67.4 mg, 64% yield, dr 12.6 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3) δ 32.52. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.50. 1 H NMR (500 MHz, CDCl3)δ 7.90 (dd, J = 11.3, 7.1 Hz, 2H), 7.84 (d, J = 7.8 Hz, 2H), 7.61 – 7.52 (m,3H), 7.49 (t, J = 7.6 Hz, 2H), 7.42 – 7.36 (m, 3H), 7.35 – 7.29 (m, 3H), 7.23(t, J = 7.2 Hz, 1H), 6.26 – 6.23 (m, 1H), 5.96 (d,J = 3.2 Hz, 1H), 3.98 (d, J = 11.8 Hz, 1H), 3.67 (d, J = 11.8 Hz, 1H), 3.13 – 2.99 (m, 3H), 2.80 (t, J = 15.7 Hz, 1H), 2.73 (d, J = 14.9 Hz, 1H), 2.56 (dd, J = 14.8, 7.2 Hz, 1H),2.53 – 2.42 (m, 2H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 151.52, 145.74 (d, J C-P =12.7 Hz), 142.65, 142.20 (d, J C-P = 4.1 Hz), 133.02 (d, J = 99.8 Hz), 132.23(d, J C-P = 2.8 Hz), 130.89 (d, J C-P = 9.2 Hz), 129.00, 128.90, 128.56, 128.44,127.53, 127.01, 126.31 (q, J C-F = 279.15 Hz) 125.68, 110.33, 108.62, 79.47,57.03, 50.14 (d, J C-P = 7.5 Hz), 43.57 (q, J C-F = 25.7 Hz), 39.71, 38.23 (d, J C-P = 59.7 Hz), 35.52 (d, J C-P= 65.7 Hz). FT-IR (KBr): 3059, 2924, 1602,1498, 1447, 1438, 1382, 1311, 1261, 1198, 1120, 1084, 1035, 1015, 969, 951,920, 885, 833, 788, 742, 698, 644, 630, 590, 515, 480 cm -1 HRMS (ESI) calcd for C 30 H 29 F3O3P + [M+H] + 525.1801, found 525.1802.

[0154] The characterization data for compound V-19 are as follows:

[0155]

[0156] Yellow oily substance (73.6 mg, 68% yield, dr 11.1 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.05. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.61. 1 H NMR (400 MHz, CDCl3)δ 7.83 – 7.78 (m, 2H), 7.76 (d, J = 7.8 Hz, 2H), 7.60 – 7.52 (m, 1H), 7.51(dd, J = 7.7, 2.6 Hz, 2H), 7.48 – 7.42 (m, 4H), 7.38 – 7.32 (m, 3H), 7.25 (t, J = 7.2 Hz, 1H), 7.18 (dd, J = 5.0, 3.0 Hz, 1H), 6.77 (d, J = 2.9 Hz, 1H), 6.71 (d, J = 5.0 Hz, 1H), 4.05 (d, J = 11.3 Hz, 1H), 3.76 (d, J= 11.3 Hz,1H), 3.12 – 2.96 (m, 3H), 2.89 (d, J = 15.1 Hz, 1H), 2.77 (t, J = 15.8 Hz,1H), 2.67 – 2.58 (m, 2H), 2.54 (dd, J = 15.5, 8.0 Hz, 1H). 13 C{ 1 H} NMR (100MHz, CDCl3) δ 146.02 (d, J C-P = 12.5 Hz), 142.84 (d, J C-P = 5.4 Hz), 139.03,133.15 (d, J C-P = 99.5 Hz), 132.16 (d, J C-P = 2.9 Hz), 130.73 (d, J C-P = 9.3Hz), 128.92 (d, J C-P = 11.8 Hz), 128.89, 128.44, 128.41, 127.10, 126.93,126.76, 125.86 (q, J C-F = 279.5 Hz), 125.84, 125.80, 121.82, 79.43 (d, J C-P =1.5 Hz), 60.36, 49.30 (d, J C-P = 8.8 Hz), 44.72 (q, J C-F = 25.9 Hz), 39.61 (d, J C-P = 3.2 Hz), 37.88 (d, J C-P = 60.7 Hz), 35.55 (d, J C-P= 65.2 Hz). FT-IR(KBr): 3059, 2948, 2868, 1497, 1447, 1438, 1382, 1310, 1261, 1197, 1167,1140, 1120, 1083, 1035, 1000, 969, 910, 833, 732, 697, 643, 593, 544, 513,479 cm -1 HRMS (ESI) calcd for C 30 H 29 F3O2PS + [M+H] + 541.1573, found 541.1575.

[0157] The characterization data for compound V-20 are as follows:

[0158]

[0159] Colorless oil (40.6 mg, 41% yield, dr 11.1 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.27. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.60. 1 H NMR (400 MHz, CDCl3)δ 7.91 (dd, J = 10.7, 7.4 Hz, 2H), 7.67 (d, J = 7.8 Hz, 2H), 7.60 – 7.53 (m,3H), 7.45 – 7.41 (m, 4H), 7.36 – 7.30 (m, 3H), 7.23 (t, J = 7.3 Hz, 1H), 5.49(ddt, J = 17.2, 10.3, 6.8 Hz, 1H), 4.95 – 4.84 (m, 2H), 3.08 (dq, J = 15.3,10.7 Hz, 1H), 3.01 – 2.91 (m, 2H), 2.89 – 2.80 (m, 2H), 2.75 (d, J = 15.9 Hz,1H), 2.70 – 2.56 (m, 3H), 2.48 (dd,J = 15.4, 7.5 Hz, 1H), 1.98 (hept, J =7.3 Hz, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 146.04 (d, J C-P = 12.6 Hz), 143.23(d, J C-P = 5.6 Hz), 135.26, 133.44 (d, J C-P = 99.5 Hz), 132.11 (d, J C-P = 2.6Hz), 130.80 (d, J C-P = 9.3 Hz), 128.92, 128.81, 128.72, 128.37, 128.14,126.90, 125.88 (q, J C-F = 279.5 Hz), 125.81, 116.49, 78.53, 61.68, 48.56 (d, J C-P = 8.7 Hz), 44.84 (q, J C-F = 25.7 Hz), 39.51, 38.97 (d, J C-P = 60.6 Hz),35.25 (d, J C-P = 65.7 Hz), 34.25. FT-IR (KBr): 3062, 2953, 2920, 2873, 1643,1498, 1446, 1386, 1314, 1264, 1188, 1117, 1066, 998, 969, 912, 863, 835, 747,732, 701, 679, 649, 589, 524, 486, 435 cm -1 . HRMS (ESI) calcd for C 29 H 31 F3O2P + [M+H] + 499.2008, found 499.2009.

[0160] The characterization data of compound V-21 are as follows:

[0161]

[0162] Yellow oily substance (60.4 mg, 54% yield, dr 10.2 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 32.23. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.58. 1 H NMR (400 MHz, CDCl3)δ 7.90 (ddd, J = 11.6, 8.0, 1.6 Hz, 2H), 7.73 (dd, J = 7.4, 1.7 Hz, 2H), 7.58– 7.50 (m, 3H), 7.45 (dt, J = 7.8, 3.8 Hz, 4H), 7.36 (td, J = 7.3, 4.9 Hz,3H), 7.30 – 7.26 (m, 2H), 7.26 – 7.20 (m, 4H), 6.20 (d, J = 16.0 Hz, 1H), 5.92 (dt, J = 15.9, 5.5 Hz, 1H), 3.66 (ddd, J = 12.5, 5.6, 1.6 Hz, 1H), 3.33(ddd, J = 12.6, 5.3, 1.7 Hz, 1H), 3.15 – 2.99 (m, 2H), 2.92 (t, J = 17.5 Hz, 2H), 2.79 (t, J = 15.6 Hz, 1H), 2.72 – 2.58 (m, 2H), 2.54 (dd, J = 15.5, 7.7Hz, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 145.99 (d, J C-P = 12.5 Hz), 142.98 (d, J C-P= 5.4 Hz), 136.76, 133.19 (d, J C-P = 99.5 Hz), 132.19 (d, J C-P = 2.9 Hz), 131.21, 130.77 (d, J C-P = 9.2 Hz), 129.01, 128.89, 128.86, 128.58, 128.47,128.34, 127.66, 126.98, 126.39, 126.07 (q, J C-F = 279.5 Hz),125.84, 125.61,79.16 (d, J C-P = 1.6 Hz), 63.20, 48.94 (d, J C-P = 9.1 Hz), 44.71 (q, J C-F = 25.3Hz), 39.60, 38.45 (d, J C-P = 60.6 Hz), 35.31 (d, J C-P = 65.2 Hz). FT-IR (KBr):3059, 3027, 2918, 2862, 2228, 1497, 1447, 1438, 1381, 1310, 1261, 1186, 1118,1070, 1034, 967, 910, 837, 734, 696, 644, 590, 528, 510, 441 cm -1 HRMS (ESI)calcd for C 34 H 33 F3O2P + [M+H] + 561.2165, found 561.2165.

[0163] Example 3 Synthesis of polysubstituted phosphorus six-membered phosphonium oxide compound VII using nitrogen as a nucleophile

[0164]

[0165] Specific experimental procedures: In a 10 mL sealed tube, add diene phosphine oxide compound II (0.2 mmol), copper tetraacetonitrile tetrafluoroborate (0.02 mmol), ligand (0.022 mmol), and 3,3-dimethyl-1-(trifluoromethyl)-1,2-benzoiodoxopentane (0.3 mmol) sequentially. The tube is purged five times under argon gas, and 1,2-dichloroethane (1 mL) and a nitrogen nucleophile (1 mmol) are added while maintaining purging. The reaction system is then sealed and the reaction is carried out at 70 °C for 12 hours. After the reaction is complete, the copper salt is removed by washing with sodium bicarbonate solution, dried, filtered, concentrated under reduced pressure, and purified by column chromatography using petroleum ether:ethyl acetate at a ratio of 4:1 to obtain compound VII.

[0166] The characterization data of compound VII-1 are as follows:

[0167]

[0168] White solid (47.9 mg, 42% yield, dr 12.1 / 1). Melting point: 249.5–253.1 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 32.83. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.55. 1 H NMR (400 MHz, CDCl3) δ 7.78 (dd, J = 13.2, 7.7 Hz, 4H), 7.60 (d, J = 8.9 Hz, 1H), 7.46 (t, J = 8.2 Hz, 2H), 7.40 (t, J = 7.4 Hz, 2H), 7.37 – 7.27 (m, 8H), 7.25– 7.15 (m, 2H), 7.12 (t, J = 7.4 Hz, 1H), 6.08 (d, J = 8.9 Hz, 1H), 4.90 (s,1H), 4.43 (dd, J = 16.4, 7.1 Hz, 1H), 3.47 (d, J = 14.9 Hz, 1H), 3.03 – 2.87(m, 3H), 2.77 (dd, 1H), 2.50 (dd, J= 14.8, 7.1 Hz, 1H), 2.37 (dq, J = 15.4,10.7 Hz, 1H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 154.69, 147.15, 146.06 (d, J C-P =3.8 Hz), 145.77 (d, J C-P = 12.1 Hz), 137.31, 133.33 (d, J C-P = 99.9 Hz), 132.01(d, J C-P = 3.0 Hz), 130.92 (d, J C-P = 9.2 Hz), 129.65, 128.95, 128.91, 128.81,127.96, 127.56, 127.36, 126.75, 125.95 (q, J C-F = 279.3 Hz), 125.76, 123.22,122.81, 113.42, 60.84, 48.74 (d, J C-P = 9.0 Hz), 43.91 (q, J C-F = 29.6, 27.2Hz), 40.18, 35.83 (d, J C-P = 64.3 Hz), 33.33 (d, J C-P = 62.7 Hz). FT-IR (KBr):3254, 3155, 3107, 3056, 2959, 1619, 1584, 1540, 1482, 1447, 1420, 1396, 1343,1253, 1228, 1185, 1140, 1115, 1035, 961, 893, 850, 825, 786, 713, 693, 650,616, 591, 525, 497, 481, 444 cm -1 . HRMS (ESI) calcd for C 34 H 31 F3N2OP+ [M+H] + 571.2121, found 571.2121.

[0169] The characterization data for compound VII-2 are as follows:

[0170]

[0171] Brown solid (36 mg, 32% yield, dr 13.9 / 1). Melting point: 191.1–192.5 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 33.01. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ -58.66. 1 H NMR (400 MHz, CDCl3) δ 7.62 -7.53 (m, 9H), 7.48 (dd, J = 12.7, 7.1 Hz, 3H), 7.41- 7.33 (m, 4H), 7.32 – 7.27 (m, 2H), 7.23 (d, J = 8.0 Hz, 1H), 7.16 (t, J =7.4 Hz, 1H), 6.17 – 6.12 (m, 1H), 6.11 (s, 1H), 4.43 (s, 1H), 3.20 – 2.97 (m,4H), 2.89 (d, J = 15.6 Hz, 1H), 2.81 (dd, J = 14.8, 11.1 Hz, 3H). 13 C NMR (100MHz, CDCl3) δ 146.13 (d, J C-P = 6.7 Hz), 145.08 (d, J C-P = 10.6 Hz), 140.51,134.36, 132.58 (d, J C-P = 99.4 Hz), 132.15 (d, J C-P = 2.7 Hz), 130.59 (d, J C-P=9.2 Hz), 129.46, 129.17, 129.01, 128.93 (d, J C-P = 11.7 Hz), 128.00, 127.56,127.43, 127.30, 126.40, 126.33, 126.30, 126.23, 125.79 (q, J C-F = 279.3 Hz),122.61, 118.89, 108.74, 60.03 (d, J C-P = 2.3 Hz), 50.40 (d, J C-P = 16.2 Hz), 47.48 (q, J C-F = 25.5 Hz), 39.42, 34.95 (d, J C-P = 64.2 Hz), 33.17 (d, J C-P =66.4 Hz). FT-IR (KBr): 3419, 3273, 3058, 2957, 1631, 1602, 1548, 1524, 1497,1472, 1447, 1438, 1382, 1329, 1253, 1221, 1185, 1141, 1118, 1088, 1070, 1033,965, 892, 839, 816, 787, 743, 713, 703, 673, 644, 619, 592, 583, 509, 494,474 cm -1 HRMS (ESI) calcd for C 35 H 32 F3NOP + [M+H] + 570.2168, found 570.2169.

[0172] The characterization data for compound VII-3 are as follows:

[0173]

[0174] Colorless oil (64 mg, 61% yield, dr 12.1 / 1). 31 P{ 1H} NMR (162 MHz, CDCl3)δ 33.40. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.55. 1 H NMR (400 MHz, CDCl3) δ 8.02(d, J = 5.0 Hz, 1H), 7.81 (dd, J = 11.5, 7.4 Hz, 2H), 7.62 – 7.51 (m, 3H),7.47 (d, J = 7.9 Hz, 2H), 7.42 – 7.34 (m, 5H), 7.31 – 7.25 (m, 3H), 7.19 (t, J = 7.3 Hz, 1H), 6.76 (s, 1H), 6.54 (dd, J = 7.1, 5.1 Hz, 1H), 6.49 (d, J =8.4 Hz, 1H), 4.29 – 4.08 (m, 2H), 3.14 (t, J = 16.1 Hz, 1H), 2.55 (d, J =14.6 Hz, 1H), 2.35 (d, J = 14.3 Hz, 1H), 2.27 (dd, J = 14.1, 7.6 Hz, 1H),2.06 (dd, J = 13.9, 4.9 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 156.90, 148.00,147.90 (d, J C-P = 11.6 Hz), 146.51 (d, J C-P = 12.7 Hz), 137.24, 132.66 (d, J C-P = 2.9 Hz), 131.99 (d, J C-P = 99.4 Hz), 130.41 (d, J C-P = 9.2 Hz), 129.14 (d, J C-P= 11.8 Hz), 128.76, 128.62, 127.20, 126.85, 126.53 (q, J C-F = 279.1 Hz),125.36, 124.82, 113.17, 109.79, 59.05 (d, J C-P = 4.6 Hz), 43.48 (d, J C-P = 6.0Hz), 42.75 (d, J C-P = 59.2 Hz), 40.79 (d, J C-P = 3.2 Hz), 40.39 (q, J C-F = 25.5Hz), 34.36 (d, J C-P = 66.6 Hz). FT-IR (KBr): 3302, 3056, 2925, 2855, 1602,1526, 1484, 1445, 1437, 1420, 1374, 1339, 1290, 1256, 1187, 1150, 1116, 1086,1052, 1035, 985, 964, 829, 773, 737, 697, 681, 580, 517, 482, 419 cm -1 HRMS(ESI) calcd for C 30 H 29 F3N2OP + [M+H] + 521.1964, found 521.1964.

[0175] The characterization data for compound VII-4 are as follows:

[0176]

[0177] Colorless oil (59 mg, 60% yield, dr 13.9 / 1). 31 P{ 1 H} NMR (202 MHz, CDCl3)δ 31.65. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.23. 1H NMR (500 MHz, CDCl3) δ 8.12(dd, J = 11.0, 7.2 Hz, 2H), 7.61 – 7.55 (m, 3H), 7.44 (d, J = 1.7 Hz, 1H),7.41 – 7.37 (m, 2H), 7.35 – 7.31 (m, 3H), 7.26 – 7.15 (m, 5H), 6.58 (d, J =2.5 Hz, 1H), 5.84 (t, J = 2.1 Hz, 1H), 3.62 (dd, J = 16.0, 6.3 Hz, 1H), 3.58– 3.49 (m, 2H), 3.31 (dq, J = 15.3, 10.5 Hz, 1H), 2.82 (t, J = 16.6 Hz, 1H),2.73 (ddd, J = 16.9, 14.6, 2.4 Hz, 1H), 2.58 (dq, J = 15.7, 10.9 Hz, 1H),2.50 (dd, J = 14.8, 7.9 Hz, 1H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 144.96 (d, J C-P = 5.2 Hz), 144.81 (d, J C-P = 12.5 Hz), 138.08, 132.71 (d, J C-P = 100.7 Hz),132.35 (d, J C-P = 2.9 Hz), 131.22 (d, J C-P = 9.4 Hz), 129.73, 128.96, 128.88(d, J C-P = 12.1 Hz), 128.53, 128.36, 126.91, 126.21, 125.87 (q, J C-F= 279.5Hz), 125.52, 106.09, 66.04, 48.00 (d, J C-P = 10.1 Hz), 44.70 (q, J C-F = 25.6Hz), 40.42, 39.83 (d, J C-P = 24.3 Hz), 32.67 (d, J C-P = 65.7 Hz). FT-IR (KBr):3059, 3030, 2944, 1498, 1448, 1438, 1425, 1387, 1313, 1256, 1189, 1160, 1121,1086, 1048, 1035, 1000, 970, 911, 831, 750, 696, 645, 620, 582, 532, 512, 482cm -1 HRMS (ESI) calcd for C 28 H 27 F3N2OP + [M+H] + 495.1808, found 495.1807.

[0178] The characterization data for compound VII-5 are as follows:

[0179]

[0180] Brown oily substance (72.9 mg, 65% yield, dr 2.3 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3)δ 33.81. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.66. 1 H NMR (400 MHz, CDCl3) δ 7.65(d, J = 7.9 Hz, 2H), 7.60 (dd, J = 11.6, 7.6 Hz, 2H), 7.48 (d, J = 8.1 Hz,2H), 7.45 – 7.35 (m, 6H), 7.32 (dd, J= 12.9, 5.7 Hz, 2H), 7.29 – 7.24 (m,1H), 6.50 (d, J = 7.4 Hz, 1H), 6.38 (t, J = 7.7 Hz, 1H), 5.76 (d, J = 7.9 Hz,1H), 4.37 (s, 1H), 4.32 (t, J = 8.7 Hz, 2H), 3.12 (d, J = 9.0 Hz, 2H), 3.09 –3.03 (m, 2H), 2.98 (d, J = 15.1 Hz, 1H), 2.84 – 2.78 (m, 2H), 2.79 – 2.62 (m,3H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 148.08, 146.20 (d, J C-P = 6.4 Hz), 144.64(d, J C-P = 11.2 Hz), 132.96 (d, J C-P = 99.1 Hz), 132.06 (d, J C-P = 3.0 Hz),130.71, 130.63, 128.92, 128.89, 128.80, 128.48, 127.35 (d, J C-P = 11.8 Hz),126.65, 126.22, 125.83 (q, J C-F = 279.2 Hz), 125.59, 120.61, 114.18, 113.43,70.90, 59.72, 50.74 (d, J C-P = 13.8 Hz), 46.66 (q, J C-F = 25.5 Hz), 39.48,35.82 (d, J C-P = 62.8 Hz), 34.00 (d, J C-P= 65.8 Hz), 30.66. FT-IR (KBr): 3407,3057, 2965, 1623, 1591, 1493, 1446, 1437, 1379, 1340, 1308, 1256, 1189, 1142,1118, 1085, 1068, 1039, 999, 964, 936, 910, 863, 834, 729, 698, 644, 590,547, 511, 491, 443 cm -1 HRMS (ESI) calcd for C 33 H 32 F3NO2P + [M+H] + 562.2117, found 562.2118.

[0181] The characterization data for compound VII-6 are as follows:

[0182]

[0183] Brown solid (58.8 mg, 57% yield, dr 12.2 / 1). Melting point: 173.4–176.3 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 33.79. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.71. 1 H NMR(500 MHz, CDCl3) δ 7.56 – 7.48 (m, 9H), 7.45 – 7.35 (m, 5H), 7.31 – 7.27 (m,1H), 6.97 (dd, J = 8.5, 7.3 Hz, 2H), 6.64 (t, J = 7.4 Hz, 1H), 5.92 (d, 2H), 4.23 (s, 1H), 3.09 (dq, J = 15.3, 10.6 Hz, 1H), 3.00 – 2.90 (m, 3H), 2.90 –2.74 (m, 3H), 2.72 (dd, 1H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 146.63 (d, JC-P =7.2 Hz), 145.07 (d, J C-P = 10.6 Hz), 143.15, 132.70 (d, J C-P = 99.4 Hz), 132.16(d, J C-P = 3.0 Hz), 130.60 (d, J C-P = 9.4 Hz), 129.38, 129.09, 128.96, 128.88,127.94, 127.23, 126.30, 126.21, 125.78 (q, J C-F = 279.3 Hz), 118.04, 115.51,59.82 (d, J C-P = 2.3 Hz), 50.22 (d, J C-P = 16.0 Hz), 47.47 (q, J C-F = 25.6 Hz), 39.36, 34.99 (d, J C-P = 64.0 Hz), 33.35 (d, J C-P = 65.8 Hz). FT-IR (KBr): 3292,3057, 2955, 2853, 1600, 1538, 1498, 1439, 1382, 1316, 1252, 1201, 1185, 1140,1085, 1035, 1001, 993, 964, 893, 878, 867, 833, 787, 747, 715, 693, 607, 550,504, 484, 441 cm -1 HRMS (ESI) calcd for C 31 H 30 F3NOP + [M+H] + 520.2012, found 520.2016.

[0184] The characterization data for compound VII-7 are as follows:

[0185]

[0186] Brown solid (79.4 mg, 66% yield, dr 8.3 / 1). Melting point: 192.2–194.7 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 32.41. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.67. 1 H NMR (400 MHz, CDCl3) δ 7.62 (dd, J = 11.6, 7.6 Hz, 2H), 7.57 – 7.49 (m, 7H), 7.44(d, J = 6.4 Hz, 3H), 7.38 (t, J = 7.6 Hz, 2H), 7.29 (t, J = 7.8 Hz, 1H), 6.76(dt, J = 15.4, 7.9 Hz, 2H), 6.04 (s, 1H), 5.81 (d, J = 7.9 Hz, 1H), 4.33 (s,1H), 3.14 – 3.04 (m, 1H), 2.99 (d, J = 15.7 Hz, 2H), 2.81 (d, J = 15.4 Hz, 2H), 2.80 – 2.63 (m, 3H). 13 C NMR (100 MHz, CDCl3) δ 145.83 (d, J C-P = 6.4 Hz), 144.82 (d, J C-P = 10.3 Hz), 144.61, 132.49 (d, J C-P = 99.6 Hz), 132.30, 130.60 (d, J C-P = 9.4 Hz), 130.27, 129.46, 129.08, 128.96, 128.06, 127.45, 126.21,126.10, 125.73 (q, J C-F= 278.8 Hz), 122.88, 120.91, 118.10, 113.76, 59.93,50.47 (d, J C-P = 16.0 Hz), 47.25 (q, J C-F = 24.9 Hz), 39.39, 35.34 (d, J C-P =63.8 Hz), 33.25 (d, J C-P = 66.4 Hz). FT-IR (KBr): 3417, 3278, 3068, 2957,1593, 1526, 1496, 1478, 1447, 1438, 1383, 1332, 1252, 1185, 1120, 1032, 1001,986, 964, 901, 873, 840, 786, 771, 752, 702, 607, 553, 517, 496, 484, 434 cm -1 HRMS (ESI) calcd for C 31 H 29 BrF3NOP + [M+H] + 598.1117, found 598.1119.

[0187] The characterization data for compound VII-8 are as follows:

[0188]

[0189] Brown oily substance (75.2 mg, 63% yield, dr 8.8 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3)δ 33.28. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –59.03. 1 H NMR (400 MHz, CDCl3) δ 7.59– 7.49 (m, 7H), 7.49 – 7.45 (m, 2H), 7.43 – 7.38 (m, 4H), 7.35 – 7.29 (m,3H), 6.79 (t, J = 7.8 Hz, 1H), 6.47 (t,J = 7.6 Hz, 1H), 5.93 (d, J = 8.2 Hz,1H), 5.16 (s, 1H), 3.07 (t, J = 17.0 Hz, 2H), 3.01 – 2.86 (m, 4H), 2.83 (d, J = 11.0 Hz, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 145.81 (d, J C-P = 7.4 Hz),144.54 (d, J C-P = 11.3 Hz), 140.92, 132.91, 132.78 (d, J C-P = 99.2 Hz), 132.16(d, J C-P = 2.8 Hz), 130.55 (d, J C-P = 9.5 Hz), 129.48, 129.23, 128.94 (d, J C-P =11.9 Hz), 127.82, 127.56, 127.43, 126.65, 126.05, 125.75 (q, J C-F = 279.3 Hz),118.71, 115.68, 110.23, 60.05 (d, J C-P = 2.3 Hz), 48.79 (q, J C-F = 25.6 Hz),48.46 (d, J C-P = 15.4 Hz), 39.17, 35.88 (d, J C-P = 63.9 Hz), 34.68 (d, J C-P=64.6 Hz). FT-IR (KBr): 3389, 3059, 3026, 2940, 1595, 1500, 1459, 1446, 1437,1405, 1377, 1318, 1261, 1186, 1142, 1114, 1086, 1067, 1034, 1021, 1000, 978,908, 866, 822, 773, 744, 697, 645, 609, 590, 551, 526, 495, 482, 442, 419 cm -1 HRMS (ESI) calcd for C 31 H 29 BrF3NOP + [M+H] + 598.1117, found 598.1119.

[0190] The characterization data for compound VII-9 are as follows:

[0191]

[0192] Brown solid (61 mg, 51% yield, dr 10.8 / 1). Melting point: 169.2–172.3 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 32.66. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –64.61. 1 H NMR (400 MHz, CDCl3) δ 7.60 (dd, J = 11.5, 7.6 Hz, 2H), 7.55 – 7.48 (m, 7H), 7.45(td, J = 7.9, 2.8 Hz, 3H), 7.37 (t, J = 7.6 Hz, 2H), 7.28 (t, J = 7.7 Hz, 1H), 7.03 (d, J = 8.6 Hz, 2H), 5.77 (d, J = 8.5 Hz, 2H), 4.28 (s, 1H), 3.15 –2.97 (m, 2H), 2.95 (d, J= 13.7 Hz, 1H), 2.87 – 2.72 (m, 4H), 2.68 (dd, J =14.6, 7.4 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 145.95 (d, J C-P = 6.5 Hz), 144.87(d, J C-P = 10.5 Hz), 142.18, 132.50 (d, J C-P = 100.2 Hz), 132.28 (d, J C-P = 2.8Hz), 131.82, 130.53 (d, J C-P = 9.4 Hz), 129.42, 129.05, 129.00 (d, J C-P = 11.9Hz), 127.99, 127.40, 126.22, 126.12, 125.71 (q, J C-F = 279.4 Hz), 116.89,109.93, 59.85 (d, J C-P = 2.2 Hz), 50.35 (d, J C-P = 16.1 Hz), 47.31 (q, J C-F =25.9 Hz), 39.37, 35.14 (d, J C-P = 63.7 Hz), 33.25 (d, J C-P = 65.3 Hz). FT-IR(KBr): 3419, 3283, 3176, 3036, 2959, 1595, 1529, 1490, 1447, 1439, 1383,1312, 1252, 1185, 1140, 1118, 1033, 1001, 965, 913, 894, 869, 827, 786, 750,703, 654, 633, 616, 573, 548, 503, 486, 445, 419 cm -1HRMS (ESI) calcd for C 31 H 29 BrF3NOP + [M+H] + 598.1117, found 598.1125.

[0193] The characterization data for compound VII-10 are as follows:

[0194]

[0195] Yellow oily substance (50 mg, 47% yield, dr 9.9 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ33.04. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.62. 1 H NMR (400 MHz, CDCl3) δ 7.62 –7.55 (m, 5H), 7.54 – 7.48 (m, 4H), 7.44 – 7.39 (m, 3H), 7.38 (d, J = 7.9 Hz, 2H), 7.29 (t, J = 7.3 Hz, 1H), 6.79 (d, J = 8.1 Hz, 2H), 5.88 (d, J = 8.4 Hz, 2H), 4.12 (s, 1H), 3.10 (dq, J = 15.3, 10.7 Hz, 1H), 2.97 (t, J = 15.7 Hz,2H), 2.95 – 2.86 (m, 1H), 2.87 – 2.76 (m, 3H), 2.72 (dd, J = 15.1, 8.3 Hz,1H), 2.16 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 146.80 (d, J C-P = 6.8 Hz), 145.10(d, J C-P = 10.8 Hz), 140.75, 132.80 (d, J C-P= 99.2 Hz), 132.06 (d, J C-P = 2.8Hz), 130.58 (d, J C-P = 9.3 Hz), 129.53, 129.26, 128.85, 128.84 (d, J C-P = 11.8Hz), 127.80, 127.19, 127.13, 126.27, 126.21, 125.77 (q, J C-F = 279.4 Hz), 115.62, 59.82 (d, J C-P = 2.3 Hz), 50.41 (d, J C-P = 15.5 Hz), 47.25 (q, J C-F =25.8 Hz), 39.37 (d, J C-P = 1.6 Hz), 35.06 (d, J C-P = 63.8 Hz), 33.38 (d, J C-P =65.7 Hz), 20.37. FT-IR (KBr): 3421, 3289, 3057, 3025, 2918, 1616, 1514, 1496,1446, 1438, 1381, 1303, 1253, 1185, 1140, 1117, 1087, 1034, 1000, 964, 910,895, 870, 815, 788, 772, 738, 702, 593, 506, 482, 442 cm -1 HRMS (ESI) calcd for C 32 H 32 F3NOP + [M+H] + 534.2168, found 534.2175.

[0196] The characterization data of compound VII-11 are as follows:

[0197]

[0198] Brown oily substance (54.1 mg, 51% yield, dr 9.4 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3)δ 33.54. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –59.01. 1 H NMR (400 MHz, CDCl3) δ 7.63– 7.53 (m, 4H), 7.53 – 7.46 (m, 5H), 7.44 – 7.36 (m, 5H), 7.31 – 7.27 (m,1H), 6.94 (d, J = 7.2 Hz, 1H), 6.74 (t, J = 7.7 Hz, 1H), 6.55 (t, J = 7.3 Hz, 1H), 5.87 (d, J = 8.0 Hz, 1H), 4.25 (s, 1H), 3.12 – 3.00 (m, 3H), 2.99 – 2.89(m, 3H), 2.85 (d, J = 15.8 Hz, 1H), 2.78 (dd, J = 14.7, 7.7 Hz, 1H), 1.29 (s,3H). 13 C NMR (100 MHz, CDCl3) δ 146.64 (d, J C-P = 7.1 Hz), 145.12 (d, J C-P =11.0 Hz), 141.23, 132.71 (d, J C-P = 99.3 Hz), 132.13 (d, J C-P = 2.9 Hz), 130.60(d, J C-P = 9.4 Hz), 130.51, 129.52, 128.99, 128.92 (d, J C-P = 12.1 Hz), 127.92,127.10, 126.38, 126.18, 126.02, 125.74 (q, JC-F = 279.3 Hz), 122.85, 117.46,114.25, 59.79 (d, J C-P = 2.4 Hz), 48.75 (q, J C-F = 25.7 Hz), 39.21, 35.77 (d, J C-P = 64.7 Hz), 34.24 (d, J C-P = 65.6 Hz), 16.50. FT-IR (KBr): 3430, 3058,3024, 2937, 1604, 1588, 1509, 1479, 1446, 1377, 1315, 1260, 1183, 1116, 1066,1034, 999, 954, 909, 876, 823, 773, 747, 700, 644, 590, 559, 526, 492, 450,419 cm -1 HRMS (ESI) calcd for C 32 H 32 F3NOP + [M+H] + 534.2168, found 534.2169.

[0199] Example 4 Synthesis of polysubstituted phosphatic six-membered cyclophosphine oxide IX with carbon as a nucleophile

[0200]

[0201] Specific experimental procedures: In a 10 mL sealed tube, add diene phosphine oxide compound II (0.2 mmol), copper tetraacetonitrile tetrafluoroborate (0.02 mmol), ligand (0.022 mmol), and 3,3-dimethyl-1-(trifluoromethyl)-1,2-benzoiodoxopentane (0.3 mmol) sequentially. The tube is purged five times under argon gas, and 1,2-dichloroethane (1 mL) and a carbon nucleophile (1 mmol) are added while maintaining purging. The reaction system is then sealed and the reaction is carried out at 70 °C for 12 hours. After the reaction is complete, the copper salt is removed by washing with sodium bicarbonate, and the mixture is dried, filtered, concentrated under reduced pressure, and purified by column chromatography using petroleum ether:ethyl acetate at a ratio of 4:1 to obtain compound IX.

[0202] The characterization data of compound IX-1 are as follows:

[0203]

[0204] Brown solid (56 mg, 57% yield, dr 11.2 / 1). Melting point: 151.3–157.5 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 29.88. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.44. 1 H NMR (400 MHz, CD3CN) δ 8.74 (s, 1H), 7.91 (dd, J = 10.7, 7.3 Hz, 2H), 7.79 (d, J = 7.8 Hz, 2H), 7.60 (dd, J = 7.1, 1.6 Hz, 1H), 7.56 (dd, J = 7.7, 2.6 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.41 – 7.33 (m, 4H), 7.26 (td, J = 7.3, 4.8Hz, 2H), 6.44 (q, J = 2.4 Hz, 1H), 5.87 (q, J = 2.9 Hz, 1H), 5.81 – 5.75 (m,1H), 3.44 (dd, J = 14.7, 2.4 Hz, 1H), 3.33 (tt, J = 15.3, 2.5 Hz, 1H), 3.09(dq, J = 15.6, 11.2 Hz, 1H), 2.77 (ddt, J = 17.2, 14.4, 2.6 Hz, 1H), 2.56 (d, J = 14.7 Hz, 1H), 2.45 (dd, J = 14.7, 7.4 Hz, 1H), 2.31 (dd, J = 15.6, 6.9Hz, 1H), 2.27 – 2.24 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 145.96 (d,J C-P = 12.4Hz), 144.43 (d, J C-P = 1.9 Hz), 140.31 (d, J C-P = 11.2 Hz), 132.96 (d, J C-P =99.0 Hz), 132.22 (d, J C-P = 2.9 Hz), 130.71 (d, J C-P = 9.0 Hz), 128.94 (d, J C-P = 11.5 Hz), 128.66, 128.62, 127.96, 127.30, 127.08, 125.96 (q, J C-F = 279.4Hz), 125.39, 118.08, 107.61, 103.71, 50.07 (d, J C-P = 7.9 Hz), 44.30 (d, J C-P =3.0 Hz), 42.35 (q, J C-F = 26.6 Hz), 40.32, 38.81 (d, J C-P = 58.9 Hz), 34.52 (d, J C-P = 65.7 Hz). FT-IR (KBr): 3330, 3217, 3060, 2959, 1758, 1716, 1647, 1600,1574, 1498, 1446, 1438, 1381, 1339, 1310, 1259, 1184, 1142, 1118, 1035, 1001,966, 915, 897, 834, 754, 699, 580, 537, 502, 472, 444, 419 cm -1 . HRMS (ESI)calcd for C 29 H 28 F3NOP + [M+H] +494.1855, found 494.1856.

[0205] The characterization data of compound IX-2 are as follows:

[0206]

[0207] Single crystal structure such as Figure 2 As shown, brown solid (66.3 mg, 61% yield, dr 13.7 / 1). Melting point: 214.3–215.5 °C. 31 P{ 1 H} NMR (162 MHz, (CD3)2SO) δ 29.72. 19 F{ 1 H} NMR (376 MHz, (CD3)2SO) δ –57.16. 1 H NMR (400 MHz, (CD3)2SO) δ 10.89 (d, J = 2.6 Hz, 1H), 8.01 (ddd, J = 16.3, 11.6, 7.2 Hz, 4H), 7.62 (d, J = 8.0 Hz, 2H), 7.58 – 7.48(m, 3H), 7.38 (t, J = 7.6 Hz, 2H), 7.32 (t, J = 7.7 Hz, 2H), 7.27 (dd, J =7.8, 5.1 Hz, 2H), 7.20 (t, J = 7.1 Hz, 2H), 7.11 (d, J = 2.6 Hz, 1H), 6.92(t, J = 7.6 Hz, 1H), 6.70 (t, J = 7.6 Hz, 1H), 3.62 (t, J = 15.1 Hz, 1H), 3.48 (d, J = 14.4 Hz, 1H), 3.15 (dq, J = 15.3, 11.3 Hz, 1H), 2.88 (d, J =14.3 Hz, 1H), 2.75 (t, J = 15.7 Hz, 1H), 2.64 (dd, J= 14.5, 7.2 Hz, 1H),2.38 (dd, J = 15.5, 7.0 Hz, 1H), 2.17 (dq, J = 15.4, 11.6 Hz, 1H). 13 C NMR (100 MHz, (CD3)2SO) δ 146.40 (d, J C-P = 12.7 Hz), 145.03, 136.88, 133.97 (d, J C-P = 97.4 Hz), 131.65 (d, J C-P = 2.5 Hz), 130.91 (d, J C-P = 9.1 Hz), 128.76,128.48 (d, J C-P = 11.3 Hz), 128.08, 127.35, 126.93 (d, J C-P = 14.3 Hz), 126.51,126.42 (q, J C-F = 279.8 Hz), 125.88, 124.13, 120.65, 120.04, 119.88, 118.15,118.03, 111.53, 49.77, 44.07 (d, J C-P = 3.4 Hz), 40.35 (q, J C-F = 24.5 Hz),36.18 (d, J C-P = 58.5 Hz), 34.51 (d, J C-P= 64.8 Hz). FT-IR (neat): 3164, 3058,2919, 1724, 1600, 1496, 1438, 1400, 1381, 1341, 1308, 1255, 1186, 1161, 1113,1070, 1000, 964, 896, 859, 836, 826, 787, 740, 697, 638, 624, 603, 558, 547,541, 530, 489, 475, 437, 427 cm -1 HRMS (ESI) calcd for C 33 H 30 F3NOP + [M+H] + 544.2012, found 544.2013.

[0208] Table 1 Single crystal data of compound IX-2

[0209]

[0210] The characterization data of compound IX-3 are as follows:

[0211]

[0212] Brown solid (68 mg, 60% yield, dr 12.6 / 1). Melting point: 157.6–165.1 °C. 31 P{ 1 H}NMR (162 MHz, CDCl3) δ 29.16. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.49. 1 H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.8 Hz, 2H), 7.84 (dd, J = 10.3, 7.5 Hz, 2H),7.55 – 7.45 (m, 3H), 7.44 – 7.35 (m, 6H), 7.29 (d, J = 6.7 Hz, 1H), 7.23 (d, J = 6.9 Hz, 1H), 7.20 (d, J = 8.2 Hz, 1H), 7.14 (d, J= 8.1 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 6.85 (t, J = 7.6 Hz, 1H), 6.80 (s, 1H), 3.72 (d, J = 15.3Hz, 1H), 3.68 (s, 3H), 3.43 (d, J = 14.4 Hz, 1H), 3.22 (dq, J = 15.6, 10.8Hz, 1H), 2.99 (t, J = 16.1 Hz, 1H), 2.75 (d, J = 14.4 Hz, 1H), 2.42 (dd, J =16.0, 6.3 Hz, 1H), 2.29 (dd, J = 14.7, 6.4 Hz, 1H), 2.12 (dq, J = 15.6, 10.8Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 146.30 (d, J C-P = 12.2 Hz), 144.82, 137.78,133.40 (d, J C-P = 98.8 Hz), 132.01 (d, J C-P = 2.9 Hz), 130.85 (d, J C-P = 8.7Hz), 128.82 (d, J C-P = 11.5 Hz), 128.68, 128.57, 128.31, 127.10, 126.98 (d, J C-P = 13.7 Hz), 126.77, 126.15 (q, J C-F = 279.5 Hz), 125.50, 125.02, 124.05,121.83, 120.53, 119.08, 109.55, 52.04 (d, J C-P = 6.9 Hz), 44.64 (d, JC-P = 3.5Hz), 41.09 (q, J C-F = 25.3 Hz), 40.80, 37.52 (d, J C-P = 58.9 Hz), 36.12 (d, J C-P = 65.8 Hz), 32.75. FT-IR (KBr): 3057, 3031, 2957, 2228, 1600, 1537, 1496,1400, 1328, 1307, 1258, 1192, 1138, 1001, 964, 927, 894, 857, 833, 810, 784,737, 643, 606, 599, 563, 547, 520, 500, 485, 461, 428 cm -1 HRMS (ESI) calcd for C 34 H 32 F3NOP + [M+H] + 558.2168, found 558.2175.

[0213] The characterization data of compound IX-4 are as follows:

[0214]

[0215] Yellow oily substance (27 mg, 24% yield, dr 8.5 / 1). 31 P{ 1 H} NMR (162 MHz, CDCl3) δ30.82. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.43. 1 H NMR (400 MHz, CDCl3) δ 7.81(dd, J = 10.3, 7.6 Hz, 2H), 7.58 – 7.47 (m, 5H), 7.34 – 7.27 (m, 5H), 7.27 –7.21 (m, 2H), 7.15 (dd, J = 10.2, 8.0 Hz, 2H), 6.37 (dd, J = 8.7, 2.6 Hz, 1H), 6.12 (d, J= 2.6 Hz, 1H), 3.72 (s, 3H), 3.66 (t, J = 16.5 Hz, 1H), 3.30– 3.15 (m, 5H), 2.87 (dd, J = 19.3, 14.7 Hz, 2H), 2.51 (dd, J = 16.1, 6.6 Hz,1H), 2.36 (dd, J = 14.8, 6.9 Hz, 1H), 2.16 (dq, J = 15.6, 11.0 Hz, 1H). 13 CNMR (100 MHz, CDCl3) δ 159.99, 158.35, 146.77, 146.08 (d, J C-P = 12.4 Hz),133.91 (d, J C-P = 98.3 Hz), 131.93 (d, J C-P = 2.7 Hz), 130.70 (d, J C-P = 8.7Hz), 130.51, 128.83 (d, J C-P = 11.4 Hz), 128.33, 127.81, 127.68, 126.84,126.10 (q, J C-F = 279.9 Hz), 125.99, 125.86, 125.59, 103.57, 100.68, 55.36,55.00, 50.96 (d, J C-P = 7.8 Hz), 46.25 (d, J C-P = 3.1 Hz), 42.42 (q, J C-F = 24.7Hz), 40.29, 36.25 (d, J C-P = 61.0 Hz), 33.82 (d, J C-P= 65.5 Hz). FT-IR (KBr):3058, 3025, 2938, 2837, 1608, 1581, 1498, 1438, 1416, 1382, 1308, 1259, 1209,1138, 1118, 1087, 1032, 964, 910, 838, 786, 733, 697, 643, 602, 574, 549,534, 504, 443, 419 cm -1 HRMS (ESI) calcd for C 33 H 33 F3O3P + [M+H] + 565.2114, found 565.2124.

[0216] The characterization data of compound IX-5 are as follows:

[0217]

[0218] Gray solid (74 mg, 62% yield, dr 14.7 / 1). Melting point: 254.4–258.4 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 29.77. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.34. 1 H NMR (500 MHz, CDCl3) δ 7.85 (dd, J = 10.3, 7.6 Hz, 2H), 7.71 (d, J = 7.8 Hz, 2H),7.59 – 7.50 (m, 3H), 7.42 – 7.35 (m, 6H), 7.29 (tt, J = 5.4, 2.9 Hz, 1H),7.27 – 7.20 (m, 3H), 7.00 (d, J = 7.9 Hz, 2H), 6.98 (d, J = 8.7 Hz, 2H), 6.90(t, J = 7.2 Hz, 1H), 6.88 (d, J= 8.8 Hz, 2H), 5.76 (s, 1H), 3.44 (d, J =14.5 Hz, 1H), 3.29 (t, J = 15.8 Hz, 1H), 3.13 (dq, J = 15.6, 10.7 Hz, 1H),2.94 (t, J = 16.1 Hz, 1H), 2.67 (d, J = 14.5 Hz, 1H), 2.30 – 2.19 (m, 2H),2.14 (dq, J = 15.5, 10.8 Hz, 1H). 13 C{ 1 H} NMR (126 MHz, CDCl3) δ 146.25 (d, J C-P = 12.1 Hz), 145.69, 143.94 (d, J C-P = 11.8 Hz), 142.82, 141.40, 133.37 (d, J C-P = 98.8 Hz), 132.13 (d, J C-P = 2.6 Hz), 130.83 (d, J C-P = 9.1 Hz), 129.41,128.92 (d, J C-P = 11.4 Hz), 128.61, 128.50, 128.42, 127.13, 126.76, 126.74,126.10 (q, J C-F = 279.4 Hz), 125.49, 121.22, 117.97, 117.27, 50.87 (d, J C-P =7.3 Hz), 47.08 (d, J C-P = 3.3 Hz), 41.37 (q, J C-F = 26.1 Hz), 40.59, 38.97 (d, J C-P = 59.1 Hz), 35.27 (d,J C-P = 65.5 Hz). FT-IR (KBr): 3267, 3183, 3056,3035, 1597, 1526, 1495, 1446, 1437, 1427, 1380, 1315, 1258, 1188, 1163, 1138,1116, 1081, 1035, 963, 842, 829, 813, 785, 748, 732, 706, 693, 592, 581, 536,510, 500 cm -1 HRMS (ESI) calcd for C 37 H 34 F3NOP + [M+H] + 596.2325, found 596.2326.

[0219] The characterization data of compound IX-6 are as follows:

[0220]

[0221] Brown solid (64 mg, 60% yield, dr 14.2 / 1). Melting point: 92.5–96.7 °C. 31 P{ 1 H} NMR (162 MHz, CDCl3) δ 29.31. 19 F{ 1 H} NMR (376 MHz, CDCl3) δ –58.46. 1 H NMR (400MHz, CDCl3) δ 7.83 (dd, J = 10.3, 7.6 Hz, 2H), 7.70 (d, J = 7.8 Hz, 2H), 7.58– 7.48 (m, 3H), 7.42 – 7.35 (m, 6H), 7.32 – 7.27 (m, 1H), 7.23 (t, J = 7.3Hz, 1H), 6.91 (d, J = 8.6 Hz, 2H), 6.42 (d, J = 8.5 Hz, 2H), 3.70 (s, 1H), 3.41 (d, J = 14.5 Hz, 1H), 3.28 (t, 1H), 3.12 (dq,J = 15.6, 10.7 Hz, 1H),2.92 (t, J = 14.7, 2.4 Hz, 1H), 2.75 (s, 3H), 2.65 (d, J = 14.5 Hz, 1H), 2.21(dd, J = 15.6, 6.7 Hz, 2H), 2.11 (dq, J = 15.6, 10.8 Hz, 1H). 13 C{ 1 H} NMR (100MHz, CDCl3) δ 147.49, 146.37 (d, J C-P = 12.5 Hz), 145.99, 140.51 (d, J C-P =12.1 Hz), 132.04 (d, J C-P = 2.8 Hz), 130.82 (d, J C-P = 8.9 Hz), 128.90, 128.79,128.56, 128.50, 128.30, 127.07, 126.62, 126.56, 126.12 (q, J C-F = 279.7 Hz),125.49, 112.16, 51.01 (d, J C-P = 7.3 Hz), 46.91 (d, J C-P = 3.6 Hz), 41.33 (q, J C-F = 25.8 Hz), 40.60 (dd, J C-F = 3.2 Hz, J C-P = 1.9 Hz), 39.05 (d, J C-P = 58.7Hz), 35.32 (d, J C-P= 65.3 Hz), 30.70. FT-IR (KBr): 3330, 3057, 3026, 2924,2813, 1614, 1521, 1497, 1446, 1437, 1382, 1325, 1307, 1255, 1194, 1118, 1088,1034, 1000, 965, 910, 837, 785, 733, 699, 679, 644, 581, 539, 502 cm -1 HRMS(ESI) calcd for C 32 H 32 F3NOP + [M+H] + 534.2168, found 534.2169.

[0222] The characterization data of compound IX-7 are as follows:

[0223]

[0224] Brown solid (75 mg, 67% yield, dr 19.0 / 1). Melting point: 148.6–153.2 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 29.72. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.36. 1 H NMR (500 MHz, CDCl3) δ 7.83 (dd, J = 10.7, 7.3 Hz, 2H), 7.70 (d, J = 7.8 Hz, 2H),7.58 – 7.48 (m, 3H), 7.39 – 7.34 (m, 6H), 7.31 – 7.26 (m, 1H), 7.23 (t, J =7.3 Hz, 1H), 6.59 (d, J = 2.2 Hz, 1H), 6.44 (dd, J = 8.4, 2.2 Hz, 1H), 6.39(d, J = 8.4 Hz, 1H), 4.15 (td, J = 4.2, 1.7 Hz, 2H), 3.38 (d, J= 14.5 Hz,1H), 3.32 (s, 2H), 3.26 (t, J = 15.8 Hz, 1H), 3.07 (dq, J = 15.6, 10.7 Hz,1H), 2.91 (t, J = 16.2 Hz, 1H), 2.57 (d, J = 14.5 Hz, 1H), 2.19 (ddd, J =21.6, 15.2, 6.2 Hz, 2H), 2.08 (dq, J = 15.8, 11.0 Hz, 1H). 13 C{ 1 H} NMR (126MHz, CDCl3) δ 146.25 (d, J C-P = 12.5 Hz), 145.51, 143.59, 142.88 (d, J C-P =12.2 Hz), 133.37 (d, J C-P = 98.8 Hz), 132.07 (d, J C-P = 2.7 Hz), 131.80, 130.83(d, J C-P = 8.7 Hz), 128.86 (d, J C-P = 11.4 Hz), 128.56, 128.47, 128.33, 127.08,126.64, 126.12 (q, J C-F = 279.7 Hz), 125.45, 118.95, 115.42, 114.05, 65.34,51.03 (d, J C-P = 7.1 Hz), 46.89 (d, J C-P = 3.3 Hz), 41.12 (q, J C-F = 25.5 Hz),40.89, 40.59, 38.85 (d, J C-P = 58.9 Hz), 35.43 (d, JC-P = 65.4 Hz). FT-IR(KBr): 3298, 3057, 3027, 2949, 2874, 1618, 1600, 1585, 1518, 1446, 1381,1353, 1306, 1256, 1190, 1117, 1040, 1000, 967, 910, 854, 830, 785, 729, 698,636, 608, 592, 546, 504 cm -1 HRMS (ESI) calcd for C 33 H 32 F3NO2P + [M+H] + 562.2117, found 562.2119.

[0225] The characterization data for compound IX-8 are as follows:

[0226]

[0227] Brown solid (50 mg, 43% yield, dr 16.7 / 1). Melting point: 129.5–132.8 °C. 31 P{ 1 H}NMR (202 MHz, CDCl3) δ 29.78. 19 F{ 1 H} NMR (471 MHz, CDCl3) δ –58.33. 1 H NMR (500 MHz, CDCl3) δ 7.82 (dd, J = 10.3, 7.7 Hz, 2H), 7.68 (d, J = 7.8 Hz, 2H),7.57 – 7.48 (m, 3H), 7.41 – 7.33 (m, 6H), 7.29 (tt, J = 5.3, 2.3 Hz, 1H), 7.22 (t, J = 7.3 Hz, 1H), 6.98 – 6.85 (m, 1H), 6.80 (d, J = 2.3 Hz, 1H), 6.48 (dd, J = 8.6, 2.4 Hz, 1H), 6.25 (d, J = 8.5 Hz, 1H), 3.52 (dd,J = 6.3, 3.6Hz, 2H), 3.34 (d, J = 14.5 Hz, 1H), 3.22 (t, J = 15.7 Hz, 1H), 3.10 (dq, J =15.6, 10.7 Hz, 1H), 2.96 (dd, J = 6.7, 3.5 Hz, 2H), 2.95 – 2.87 (m, 1H), 2.57(d, J = 14.5 Hz, 1H), 2.21 (dd, J = 14.7, 6.4 Hz, 1H), 2.15 (dd, J = 15.9,6.0 Hz, 1H), 2.10 – 2.01 (m, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl3) δ 146.17 (d, J C-P = 12.4 Hz), 145.58, 141.49 (d, J C-P = 12.0 Hz), 139.85, 133.34 (d, J C-P =98.6 Hz), 132.04, 130.77 (d, J C-P = 8.8 Hz), 128.84 (d, J C-P = 11.4 Hz),128.55, 128.43, 128.29, 127.07, 126.59, 126.08 (q, J C-F = 279.4 Hz), 125.45,124.02, 123.98, 115.45, 115.27, 50.86 (d, J C-P = 7.1 Hz), 46.86 (d, J C-P = 3.4Hz), 42.19, 41.22 (q, J C-F = 24.1 Hz), 40.54, 38.94 (d, J C-P= 58.6 Hz), 35.15(d, J C-P = 65.5 Hz), 25.99. FT-IR (KBr): 3309, 3057, 3025, 2928, 2851, 1601,1506, 1446, 1381, 1354, 1311, 1255, 1190, 1116, 1033, 1000, 965, 909, 829,785, 697, 644, 600, 586, 545, 502, 442 cm -1 HRMS (ESI) calcd for C 33 H 32 F3NOPS + [M+H] + 578.1889, found 578.1890.

[0228] Application example: A trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphonooxide was used as a catalyst to catalyze the Appel reaction to synthesize compound 2, wherein the Appel reaction is as follows:

[0229]

[0230] The catalysts used were compounds V-1, V-4, V-5, and V-6 provided in the embodiments of the present invention, with a dosage of 2 mol%.

[0231] The catalysts used were compounds V-2, V-11, VII-6, IX-3 and IX-6 provided in the embodiments of the present invention, with a dosage of 5 mol%.

[0232] Experimental Procedure: Weigh the catalyst (0.01 mmol or 0.02 mmol) into a 10 mL sealed tube. Vacuum the tube five times under argon purging. Add ultra-dry toluene (1 mL), phenyl ethylene oxide (0.2 mmol), phenylsilane (0.3 mmol), and hexachloroacetone (0.28 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.

[0233] Following the steps described above, this invention selects various types of six-membered phosphorus phosphine oxides obtained from the preparation as catalysts, demonstrating the structure-activity relationship between the substituent type in the phosphorus six-membered ring structure and the catalytic effect in the Appel catalytic reaction. The catalytic results are shown in Table 2 below:

[0234] Table 2 Structure-activity relationship between substituent type in the phosphorus six-membered ring structure and catalytic effect in Appel catalysis.

[0235]

[0236] The catalytic reaction results described in the table demonstrate that multi-substituted phosphonohexacyclic phosphonooxides can achieve good catalytic performance in the Appel reaction, and various phosphonohexacyclic skeletal structures are applicable. Compared with previously reported phosphonooxides as catalysts [ J. Org. Chem 2019, 84 [7863-7870], under the condition of consistent reaction substrates, 10 mol% is required to achieve the Appel reaction of phenyl ethylene oxide, while the catalyst amount of polysubstituted phosphata six-membered ring phosphonium oxide can be reduced to 2-5 mol% and still obtain good catalytic effect, indicating that the catalytic efficiency of the catalyst based on the framework structure of the polysubstituted phosphata six-membered ring phosphonium oxide is significantly improved; this result is close to the Appel catalytic ability of the currently known best phosphata four-membered ring phosphonium oxide catalyst. Org. Lett. 2023, 25 [9114-9118]. The phosphorus-hexa-ring skeletal phosphine oxides reported in this patent have better preparation versatility and scalability, which makes the further development of this type of phosphorus-hexa-ring skeletal phosphine oxide catalyst promising and expands the catalyst synthesis, laying a good foundation for further exploration of the development and application of various types of phosphorus-hexa-ring phosphine oxide catalysts.

[0237] 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 polysubstituted phosphatic six-membered ring phosphonium oxide compound containing trifluoromethyl, characterized in that, Includes any one of the following structural formulas (1), (2), and (3): ； In the general structural formula (1): Ar 1 It is a benzene ring, benzo-1,3-dioxolane ring, or naphthalene ring; n is an integer, n is 0, 1, or 2; R 1 It can be hydrogen, halogen atom, trifluoromethyl, C1~C6 saturated alkoxy or C1~C6 saturated alkyl; R 2 It is a phenyl group; wherein the hydrogen atom on the phenyl group can be replaced by a C1~C3 saturated alkyl or halogen atom; R 3 It is hydrogen, C1~C6 saturated alkyl, C1~C6 cycloalkyl, benzyl, phenyl, , , , or ; In the general structural formula (2): Ar 1’ It is phenyl; R 1’ It is hydrogen or a C1~C3 saturated alkyl group; R 2’ It is phenyl; R 4 For phenyl, substituted phenyl, , , or ; The substituted phenyl group is formed when the hydrogen atom on the phenyl group is replaced by a C1~C3 saturated alkyl or halogen atom; In the general structural formula (3): Ar 1” It is phenyl; R 1” It is hydrogen or a C1~C3 saturated alkyl group; R 2” It is phenyl; R 5 for , , , , , , , or .

2. The trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphonium oxide compound according to claim 1, characterized in that, In the general structural formula (1): Ar1 is a benzene ring, benzo-1,3-dioxolane ring, or naphthalene ring; n is an integer, n is 0, 1, or 2; R1 is hydrogen, a halogen atom, trifluoromethyl, a C1-C3 saturated alkoxy, or a C1-C3 saturated alkyl; R2 is phenyl; wherein the hydrogen atom of the phenyl may be substituted by a bromine or chlorine atom; R3 is hydrogen, a C1-C3 saturated alkyl, cyclohexyl, benzyl, phenyl, , , , or ; In the structural formula (2): Ar 1’ It is phenyl; R 1’ It is hydrogen or a C1~C3 saturated alkyl group; R 2’ It is phenyl; R 4 For phenyl, substituted phenyl, , , or The substituted phenyl group is formed when the hydrogen atom on the phenyl group is replaced by a C1-C3 saturated alkyl or halogen atom; the halogen atom is bromine or chlorine. In the general structural formula (3): Ar 1” It is phenyl; R 1” It is hydrogen or a C1~C3 saturated alkyl group; R 2” It is phenyl; R 5 for , , , , , , , or .

3. The use of the trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphonooxide compound according to any one of claims 1-2 in the Appel reaction.

4. The application according to claim 3, characterized in that, A trifluoromethyl-containing polysubstituted phosphatic six-membered ring phosphonooxide 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... .

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