A method of photocatalytic deoxygenation of alcohols

Abstract

The application discloses a method for photocatalytic alcohol deoxygenation conversion, which comprises the following steps: under the protection of inert gas, alcohol compound, photocatalyst, reducing agent, condensing agent, diphenyl chlorophosphine, alkali, molecular sieve and super-dry solvent are fully mixed, then olefin or aryl iodine and elemental iodine are added into the mixture, and the mixture is stirred and reacted under the irradiation of light to obtain alcohol deoxygenation alkylization product or alcohol deoxygenation arylation product; when the alcohol deoxygenation arylation product is prepared, a metal catalyst and a ligand also need to be added. The method uses non-activated alcohol which is cheap and easy to obtain as an initial raw material, greatly reduces the reaction steps and improves the efficiency; by using the method, multi-functionalization of a multi-alcohol substrate can be realized, and rapid synthesis of a drug intermediate can also be realized, so that the application prospect is good.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and to a method for photocatalytic deoxygenation conversion of alcohols. Background Technology

[0002] Because alcohols are carbon coupling precursors with a wide range of applications, the development of alcohol deoxyfunctionalization has attracted much attention in recent years. Activating alcohols with inexpensive and readily available trivalent phosphine is an ideal method for alcohol activation, but there is currently no mature process for activating alcohols with trivalent phosphine.

[0003] Therefore, developing a low-cost and highly efficient process for activating trivalent phosphine alcohols is of great practical significance. Summary of the Invention

[0004] Due to the deficiencies of existing technologies, this invention provides a low-cost and highly efficient trivalent phosphine-activated alcohol process, specifically a novel photocatalytic alcohol deoxygenation conversion method. This process uses simple reaction substrates, inexpensive and readily available activators, and has high reaction efficiency.

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

[0006] A method for photocatalytic deoxyalkylation of alcohols involves thoroughly mixing an alcohol compound, a photocatalyst, a reducing agent, a condensing agent, diphenylchlorophosphine, a base, a molecular sieve, and an ultra-dry solvent under an inert gas atmosphere. An olefin and elemental iodine are then added sequentially, and the mixture is stirred under light irradiation to obtain the deoxyalkylated alcohol product. This method can be used for the deoxyalkylation modification of the steroid hormone drug epiandrolone (as shown in Example 3).

[0007] The reaction equations for alkylation and arylation are shown in Formula V and Formula VI, respectively:

[0008]

[0009] This invention first utilizes the very inexpensive diphenylchlorophosphine to condense in situ with an alcohol to obtain a trivalent phosphine oxide intermediate, which then reacts with iodine and is further coupled with an olefin or aryl iodine to obtain a functionalized product. Compared with existing technologies, this invention provides a novel alcohol deoxygenation conversion method (proposed for the first time in this invention). The method of this invention has many advantages, such as good substrate universality, inexpensive and readily available activators, high reaction efficiency, and mild reaction. In addition, the method of this invention can be applied to the synthesis of drug molecules and also provides a synthetic route for the sequential deoxygenation functionalization of polyol compounds, showing good application prospects.

[0010] As a preferred technical solution:

[0011] In the photocatalytic deoxyalkylation method for alcohols described above, the inert gas refers to nitrogen, helium, or argon; thorough mixing refers to stirring for at least 20 minutes; the light refers to visible light with a wavelength of 400-780 nm; the reaction time is 0.1-72 hours; the alcohol compound includes primary alcohols, secondary alcohols, tertiary alcohols, or their isotopic substitutes; and the condensing agent is 4-dimethylaminopyridine (DMAP).

[0012] After the reaction, the reaction product is quenched, washed, extracted and dried, and then separated by a chromatography column to obtain the alcohol deoxyalkylated product.

[0013] The photocatalytic deoxyalkylation method for alcohols as described above, wherein the base is one or more of cesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium phosphate, dipotassium hydrogen phosphate, lithium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, lithium methoxide, sodium methoxide, potassium methoxide, sodium acetate, cesium acetate, cesium fluoride, triethylamine, trimethylamine, diisopropylamine, diisopropylmethylamine, dicyclohexylamine, dicyclohexylmethylamine, dimethylamine, diethylamine, dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and tetramethylguanidine (TMG);

[0014] The molecular sieve is a 3Å molecular sieve, a 4Å molecular sieve, or a 5Å molecular sieve.

[0015] The ultra-dry solvent is one or more of the following: 1,4-dioxane, N,N'-dimethylacetamide, 1,2-dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, acetone, toluene, benzene, thylbenzene, xylene, ethyl acetate, methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, methyl formate, ethyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, benzyl formate, ethyl acetoacetate, diethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, 3-methylfuran, dioxolane, methyl tert-butyl ether, anisole, tetrahydropyran, N-methylpyrrolidone, and methylcyclopentyl ether.

[0016] The reaction temperature is -40~80℃, and the time is 0.1~72h;

[0017] The photocatalyst is one of the following: 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN), ruthenium tripyridine chloride hexahydrate Ru(bpy)3Cl2·6H2O, tris(2-(4-trifluoromethylphenyl)pyridine)iridium fac-Ir(ppy)3, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile (3DPAFIPN), 2,3,5,6-tetra(9-carbazolyl)-terephthalonitrile (4CzTPN), and photosensitizers modified with such a core framework;

[0018] The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (HEH), zinc (Zn), manganese (Mn), magnesium (Mg), tetrakis(dimethylamino)ethylene (TDEA), or pinacol diboronate (B2Pin2).

[0019] The light is provided by 10-40W blue light, ultraviolet light or energy-saving lamp (CFL);

[0020] The base is 10-600% molar equivalent of the alcohol compound;

[0021] The reducing agent is 100-600% molar equivalent of the alcohol compound;

[0022] The photocatalyst is 0.01% to 10% molar equivalent of the alcohol compound;

[0023] The condensing agent is 5% to 20% molar equivalent of the alcohol compound;

[0024] The molar ratio of the alcohol to the olefin is 1:5 to 5:1;

[0025] The diphenylchlorophosphine is 100-600% molar equivalent of the alcohol compound;

[0026] The molecular sieve is present in quantities of 0.1 to 1000 grams per mole;

[0027] The elemental iodine is 10-300% molar equivalent of the alcohol compound;

[0028] The concentration of the alcohol compound in the mixture is 0.0001~1 mol / L.

[0029] In the photocatalytic deoxyalkylation method of alcohols described above, the base is one or more of cesium carbonate and potassium phosphate;

[0030] The molecular sieve is a 4Å molecular sieve;

[0031] The ultra-dry solvent is ethylene glycol dimethyl ether;

[0032] The reaction temperature is 15~30℃;

[0033] The photocatalyst is 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4CzIPN);

[0034] The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (HEH).

[0035] The light is provided by a 30W blue light lamp;

[0036] The base is 200-500% molar equivalent of the alcohol compound;

[0037] The reducing agent is 150-300% molar equivalent of the alcohol compound;

[0038] The photocatalyst is 1% to 2% molar equivalent of the alcohol compound;

[0039] The molar ratio of the alcohol to the olefin is 1:3 to 2:1;

[0040] The diphenylchlorophosphine is 110% molar equivalent of the alcohol compound;

[0041] The molecular sieve is 500 grams per mole;

[0042] The elemental iodine is 100% molar equivalent of the alcohol compound.

[0043] As described above, in a photocatalytic deoxyalkylation method for alcohols, the olefin has the chemical formula shown in Formula I:

[0044]

[0045] In Formula I, R1 is a hydrogen atom or an aryl group, and R2 and R3 are independently selected from two of the following: hydrogen atom, halogen atom, alkyl acrylate, benzyl acrylate, aryl acrylate, acrylonitrile, acrolein, acrylone, sulfone, and propylene phosphate.

[0046] Furthermore, this invention also provides a method for photocatalytic deoxyarylation of alcohols. Under inert gas protection, an alcohol compound, a photocatalyst, a metal catalyst, a ligand, a reducing agent, a condensing agent, diphenylchlorophosphine, a base, a molecular sieve, and an ultra-dry solvent are thoroughly mixed. Then, aryl iodine and elemental iodine are added sequentially, and the reaction is carried out under light irradiation with stirring to obtain the deoxyarylated alcohol product. This method can achieve the rapid synthesis of key intermediates of interleukin-2-induced T-cell kinase (as in Example 8).

[0047] As a preferred technical solution:

[0048] In the photocatalytic deoxyarylation method for alcohols described above, the inert gas refers to nitrogen, helium, or argon; the thorough mixing refers to stirring for at least 20 minutes; the light refers to visible light with a wavelength of 400-780 nm; the stirring reaction time is 0.1-72 hours; the alcohol compound includes primary alcohols, secondary alcohols, tertiary alcohols, or their isotopic substitutes; and the condensing agent is 4-dimethylaminopyridine (DMAP).

[0049] After the reaction, the reaction product is quenched, washed, extracted and dried, and then separated by chromatography to obtain the alcohol deoxyarylated product.

[0050] The photocatalytic deoxyarylation method for alcohols as described above, wherein the base is one or more of cesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium phosphate, dipotassium hydrogen phosphate, lithium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, lithium methoxide, sodium methoxide, potassium methoxide, sodium acetate, cesium acetate, cesium fluoride, triethylamine, trimethylamine, diisopropylamine, diisopropylmethylamine, dicyclohexylamine, dicyclohexylmethylamine, dimethylamine, diethylamine, dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and tetramethylguanidine (TMG);

[0051] The molecular sieve is a 3Å molecular sieve, a 4Å molecular sieve, or a 5Å molecular sieve.

[0052] The ultra-dry solvent is one or more of the following: 1,4-dioxane, N,N'-dimethylacetamide, 1,2-dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, acetone, toluene, benzene, thylbenzene, xylene, ethyl acetate, methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, methyl formate, ethyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, benzyl formate, ethyl acetoacetate, diethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, 3-methylfuran, dioxolane, methyl tert-butyl ether, anisole, tetrahydropyran, N-methylpyrrolidone, and methylcyclopentyl ether.

[0053] The reaction temperature is -40~80℃, and the time is 0.1~72h;

[0054] The photocatalyst is one of the following: 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN), ruthenium tripyridine chloride hexahydrate Ru(bpy)3Cl2·6H2O, tris(2-(4-trifluoromethylphenyl)pyridine)iridium fac-Ir(ppy)3, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate) [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile (3DPAFIPN), 2,3,5,6-tetra(9-carbazolyl)-terephthalonitrile (4CzTPN), and photosensitizers modified with such a core framework;

[0055] The metal catalyst is nickel bromide in ethylene glycol dimethyl ether (NiBr2·DME), bis-(1,5-cyclooctadiene) nickel Ni(COD)2, nickel acetylacetonate Ni(acac)2, nickel chloride in ethylene glycol dimethyl ether (NiCl2·DME), nickel bromide, nickel chloride, nickel iodide, nickel trifluoromethanesulfonate Ni(OTf)2, palladium chloride (PdCl2), copper trifluoromethanesulfonate Cu(OTf)2, or cobalt acetylacetonate Co(acac)2;

[0056] The ligands are 4,4'-di-tert-butyl-2,2'-bipyridine (dtbpy), 4,4'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 4,4'-diethyl bisphosphate-2,2'-bipyridine, 2,2'-dimethyl-2,2'-bipyridine, 3,3'-dimethyl-2,2'-bipyridine, 2,2'-bipyridine, 1,10-o-phenanthroline, terpyridine, 4,7-dimethyl-1,10-o-phenanthroline, 4,7-diphenyl-1,10-o-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,2':6',2 "-Tripyridine, 4,4',4''-tritert-butyl-2,2':6',2''-tripyridine, 2,6-bis(1-pyrazolyl)pyridine, triphenylphosphine, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, bis(diphenylphosphine)ferrocene, (S)-4-isopropyl-2-(pyridin-2-yl)-4,5-dihydrooxazole, bis((S)-4-phenyl-4,5-dihydrooxazol-2-yl)methane or (S)-2-(2-(diphenylphosphine)phenyl)-4-isopropyl-4,5-dihydrooxazole;

[0057] The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (HEH), zinc (Zn), manganese (Mn), magnesium (Mg), tetrakis(dimethylamino)ethylene (TDEA), or pinacol diboronate (B2Pin2).

[0058] The light is provided by 10-40W blue light, ultraviolet light or energy-saving lamp (CFL);

[0059] The base is 10-600% molar equivalent of the alcohol compound;

[0060] The reducing agent is 100-600% molar equivalent of the alcohol compound;

[0061] The photocatalyst is 0.01% to 10% molar equivalent of the alcohol compound;

[0062] The condensing agent is 5% to 20% molar equivalent of the alcohol compound;

[0063] The metal catalyst is 0.01% to 100% molar equivalent of the alcohol compound;

[0064] The ligand is 0.012% to 120% molar equivalent of the alcohol compound;

[0065] The molar ratio of the alcohol compound to the aryl iodine is 1:5 to 5:1;

[0066] The diphenylchlorophosphine is 100-600% molar equivalent of the alcohol compound;

[0067] The molecular sieve has a concentration of 0-1000 g per mole;

[0068] The elemental iodine is 10-300% molar equivalent of the alcohol compound;

[0069] The concentration of the alcohol compound in the mixture is 0.0001~1 mol / L.

[0070] In the photocatalytic deoxyarylation method of alcohols described above, the base is potassium phosphate;

[0071] The molecular sieve is a 4Å molecular sieve;

[0072] The ultra-dry solvent is ethyl acetate;

[0073] The reaction temperature is 15~30℃;

[0074] The photocatalyst is 4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4CzIPN);

[0075] The metal catalyst is nickel ethylene glycol dimethyl ether bromide (NiBr2·DME);

[0076] The ligand is 4,4'-di-tert-butyl-2,2'-bipyridine (dtbpy);

[0077] The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (HEH).

[0078] The light is provided by a 30W blue light lamp;

[0079] The base is 300% molar equivalent of the alcohol compound;

[0080] The reducing agent is 250% molar equivalent of the alcohol compound;

[0081] The photocatalyst is 1% to 2% molar equivalent of the alcohol compound;

[0082] The metal catalyst is 5% molar equivalent of the alcohol compound;

[0083] The ligand is 6% molar equivalent of the alcohol compound;

[0084] The molar ratio of the alcohol compound to the aryl iodine is 1:1.5;

[0085] The diphenylchlorophosphine is 110% molar equivalent of the alcohol compound;

[0086] The molecular sieve is 500 grams per mole;

[0087] The elemental iodine is 100% molar equivalent of the alcohol compound.

[0088] As described above, in a photocatalytic deoxyarylation method for alcohols, the chemical formula of the aryl iodine is shown in Formula II or Formula III:

[0089]

[0090] In Formula II, R1 is a methyl, methoxy, cyano, aldehyde, ester, ketone, trifluoromethyl, or halogen atom;

[0091]

[0092] In Formula III, R1, R2, R4, and R5 are independently selected from one of the following: methoxy group, ester group, fluorine atom, chlorine atom, bromine atom, and hydrogen atom, and R3 is (trimethylsilyl)ethoxymethyl.

[0093] The structures of DMAP, HEH, and 4CzIPN mentioned above are as follows:

[0094]

[0095] The above invention has the following advantages or beneficial effects:

[0096] (1) The photocatalytic alcohol deoxygenation conversion method of the present invention uses inexpensive and readily available non-activated alcohols as starting materials, which greatly reduces the synthesis steps and improves the synthesis efficiency;

[0097] (2) The photocatalytic alcohol deoxygenation conversion method of the present invention uses inexpensive diphenylchlorophosphine as an activator, which greatly reduces the synthesis cost;

[0098] (3) The photocatalytic alcohol deoxygenation conversion method of the present invention, compared with the existing synthesis method, utilizes the excitation of external free radicals to generate trivalent phosphine free radicals, which makes the substrate more universal and can be conveniently applied to the synthesis of drug intermediates and the multifunctional conversion of polyol compounds, with good application prospects. Detailed Implementation

[0099] The present invention will be further described below with reference to specific embodiments, but these are not intended to limit the invention.

[0100] Example 1

[0101]

[0102] In a nitrogen-filled glove box, DMAP (0.02 mmol, 10 mol%), 4CzIPN (0.004 mmol, 2 mol%), HEH (0.6 mmol), K3PO4 (1.0 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and DME (2.0 mL) was added. Alcohol was then added. 0.2 mmol of PPh₂Cl and 0.22 mmol of Cy₂NH₄⁺ were added to the above mixture, and the mixture was stirred for 20 minutes on a magnetic stirrer set to 1000 rpm. Then, 0.2 mmol of iodine and benzyl acrylate were added. (0.6 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0408 g of the target product. Its yield is 77%.

[0103] The above products were characterized as follows:

[0104] 1 H NMR (400 MHz, CDCl3) δ 7.39 - 7.30 (m, 5H), 5.11 (s, 2H), 3.66 (s,3H), 2.45 - 2.38 (m, 3H), 2.18 - 2.12 (m, 1H), 2.05 - 1.93 (m, 1H), 1.76 -1.66 (m, 1H), 1.60 - 1.51 (m, 1H), 0.95 (d, J = 6.8 Hz, 3H);

[0105] 13 C NMR (101 MHz, CDCl3) δ 173.3, 173.1, 136.0, 128.5, 128.2, 66.2,51.4, 41.2, 31.9, 31.5, 29.9, 19.3;

[0106] HRMS: m / z (ESI) calculated [M+H] + : 265.1434, measured: 265.1439.

[0107] Example 2

[0108]

[0109] In a nitrogen-filled glove box, DMAP (0.02 mmol, 10 mol%), 4CzIPN (0.004 mmol, 2 mol%), HEH (0.6 mmol), K3PO4 (1.0 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and DME (2.0 mL) was added. Alcohol was then added. 0.2 mmol of PPh₂Cl and 0.22 mmol of Cy₂NH₄⁺ were added to the above mixture, and the mixture was stirred for 20 minutes on a magnetic stirrer set to 1000 rpm. Then, 0.2 mmol of iodine and phenyl acrylate were added. (0.6 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0354 g of the target product. Its yield is 61%.

[0110] The above products were characterized as follows:

[0111] 1 H NMR (400 MHz, CDCl3) δ 7.40 - 7.35 (m, 2H), 7.24 - 7.20 (m, 1H), 7.09 - 7.05 (m, 2H), 3.94 (s, 4H), 2.58 (t, J = 7.6 Hz, 2H), 1.81 - 1.39 (m,6H), 1.59 - 1.51 (m, 2H); 1.41 - 1.26 (m, 3H);

[0112] 13 C NMR (101 MHz, CDCl3) δ 172.3, 150.7, 129.3, 125.7, 121.5, 108.9, 64.2, 64.2, 35.9, 34.2, 32.2, 31.1, 29.8.

[0113] HRMS: m / z (ESI) calculated [M+H] + : 291.1591, measured: 291.1598.

[0114] Example 3

[0115]

[0116] In a nitrogen-filled glove box, DMAP (0.02 mmol, 10 mol%), 4CzIPN (0.004 mmol, 2 mol%), HEH (0.6 mmol), K3PO4 (1.0 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and DME (2.0 mL) was added. Alcohol was then added. 0.2 mmol of PPh₂Cl and 0.22 mmol of Cy₂NH₄⁺ were added to the above mixture, and the mixture was stirred for 20 minutes on a magnetic stirrer set to 1000 rpm. Then, 0.2 mmol of iodine and benzyl acrylate were added. (0.6 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0413 g of the target product. Its yield was 47% (dr = 2.6:1).

[0117] The above products were characterized as follows:

[0118] 1 H NMR (400 MHz, CDCl3) δ 7.38 - 7.29 (m, 5H), 5.10 (s, 2H), 2.45 -2.31 (m, 3H), 2.10 - 2.01 (m, 1H), 1.95 - 1.88 (m, 1H), 1.79 - 1.60 (m, 6H),1.58 - 1.35 (m, 5H), 1.29 - 1.18 (m, 6H), 1.13 - 0.90 (m, 4H), 0.84 (s, 3H),0.80 (s, major, 2.26H), 0.76 (s, minor, 0.87H), 0.73 - 0.64 (m, 1H);

[0119] 13 C NMR (101 MHz, CDCl3) δ 221.1, 173.7, 173.7, 136.0, 136.0, 128.4,128.1, 128.0, 128.0, 66.0, 65.9, 54.7, 54.6, 54.1, 54.1, 51.5, 51.4, 47.7,46.4, 40.2, 38.3, 37.4, 36.5, 36.1, 35.7, 35.1, 35.0, 35.0, 33.0, 32.9, 32.6,32.5, 32.1, 31.8, 31.5, 30.9, 30.8, 28.5, 28.5, 28.4, 27.0, 25.1, 21.7, 21.6, 20.2, 19.9, 13.7, 12.2, 11.6;

[0120] HRMS: m / z (ESI) calculated [M+H] +: 437.3050, measured: 437.3056.

[0121] Example 4

[0122]

[0123] In a nitrogen-filled glove box, DMAP (0.02 mmol, 10 mol%), 4CzIPN (0.004 mmol, 2 mol%), HEH (0.6 mmol), K3PO4 (1.0 mmol), and 4ÅMS (100 mg) were placed into oven-dried 10 mL Schlenk tubes equipped with magnetic stirrers, and DME (2.0 mL) was added. Alcohol was then added. 0.2 mmol of PPh₂Cl and 0.22 mmol of Cy₂NH₄⁺ were added to the above mixture, and the mixture was stirred for 20 minutes at 1000 rpm using a magnetic stirrer. Then, 0.2 mmol of iodine and benzyl acrylate were added. (0.6 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0237 g of the target product. Its yield is 52%.

[0124] The above products were characterized as follows:

[0125] 1 H NMR (400 MHz, CDCl3) δ 7.39 - 7.30 (m, 5H), 5.80 (tt, J = 56.8 Hz, 3.6 Hz, 1H), 5.12 (s, 2H), 2.43 (t, J = 7.2 Hz, 2H), 1.94 - 1.77 (m, 4H);

[0126] 13 C NMR (101 MHz, CDCl3) δ 172.5, 135.8, 128.6, 128.3, 128.2, 116.8(t, J = 240.0 Hz), 66.3, 33.3 (t, J = 11.8 Hz), 17.5 (d, J = 6.0 Hz);

[0127] HRMS: m / z (ESI) calculated [M+Na] + : 251.0854, measured: 251.0883.

[0128] Example 5

[0129]

[0130] In a nitrogen-filled glove box, DMAP (0.02 mmol, 10 mol%), 4CzIPN (0.004 mmol, 2 mol%), HEH (0.6 mmol), Cs₂CO₃ (0.6 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and DME (2.0 mL) was added. CD₃OD (0.2 mmol), PPh₂Cl (0.22 mmol), and Cy₂NH (0.24 mmol) were added to the above mixture, and the mixture was stirred for 20 minutes at 1000 rpm with a magnetic stirrer. Then, iodine (0.2 mmol) and... (0.6 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0146 g of the target product. Its yield is 42%.

[0131] The above products were characterized as follows:

[0132] 1 H NMR (400 MHz, CDCl3) δ 7.44 - 7.32 (m, 5H), 3.20 (s, 2H);

[0133] 13 C NMR (101 MHz, CDCl3) δ 131.9, 130.2, 128.8, 115.9, 44.4, 32.9,24.0, 23.4 (m);

[0134] HRMS: m / z (ESI) calculated [M+H] + : 174.1105, measured: 174.1128.

[0135] Example 6

[0136]

[0137] In a nitrogen-filled glove box, DMAP (0.04 mmol, 20 mol%), 4CzIPN (0.004 mmol, 2 mol%), HEH (0.6 mmol), Cs2CO3 (0.6 mmol), and 4 Å MS (100 mg) were loaded into a 10 mL oven-dried Schlenk tube equipped with a magnetic stir bar, and DME (2.0 mL) was added. (0.4 mmol), PPh2Cl (0.44 mmol), and Cy2NH (0.48 mmol) were added to the above mixture, and the mixture was stirred for 20 minutes under a magnetic stirrer set at 1000 rpm. Then, iodine (0.4 mmol) and benzyl acrylate (0.2 mmol) were added. The sealed Schlenk tube was placed under a magnetic stirrer at 1000 rpm and irradiated under blue light (λ = 450 - 455 nm) for 12 hours. The reaction solution was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to obtain 0.0207 g of the target product , with a yield of 34%.

[0138] The above product was characterized as follows:

[0139] 1 H NMR (400 MHz, CDCl3) δ 7.39 - 7.31 (m, 5H), 5.67 (ddd, J = 17.2 Hz, 10.0 Hz, 7.6 Hz, 1H), 5.11 (s, 2H), 4.96 - 4.88 (m, 2H), 2.32 - 2.28 (m, 2H), 2.13 - 2.06 (m, 1H), 1.59 - 1.54 (m, 2H), 1.25 - 1.11 (m, 6H), 5.67 (dd, J = 6.8 Hz, 3H), 0.83 (s, 6H);

[0140] 13C NMR (101 MHz, CDCl3) δ 174.3, 144.8, 136.1, 128.5, 128.2, 128.2,112.4, 66.2, 41.8, 37.7, 37.5, 36.5, 32.5, 29.7, 26.8, 21.5, 20.3;

[0141] HRMS: m / z (ESI) calculated [M+Na] + : 325.2135, measured: 325.2138.

[0142] Example 7

[0143]

[0144] In a nitrogen-filled glove box, DMAP (0.04 mmol, 20 mol%), 4CzIPN (0.004 mmol, 2 mol%), NiBr2(dtbpy) (0.01 mmol, 5 mol%), HEH (0.5 mmol), K3PO4 (0.6 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and EA (3.0 mL) was added. Add 0.2 mmol of PPh₂Cl (0.22 mmol) and Cy₂NH₄⁺ (0.24 mmol) to the above mixture, and stir the mixture for 20 minutes on a magnetic stirrer set to 1000 rpm. Then add 0.2 mmol of iodine and (0.3 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0537 g of the target product. Its yield is 74%.

[0145] The above products were characterized as follows:

[0146] 1H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 7.86 - 7.83 (m, 4H), 7.54 -7.53 (m, 1H), 7.40 - 7.36 (m, 2H), 4.31 - 4.25 (m, 2H), 2.90 - 2.81 (m, 1H),1.79 - 1.57 (m, 4H), 1.32 (d, J = 7.2 Hz, 3H);

[0147] 13 C NMR (101 MHz, CDCl3) δ 191.8, 164.2, 154.2, 135.2, 134.9, 133.1,132.7, 130.1, 127.9, 127.6, 65.6, 40.0, 34.1, 26.7, 22.0;

[0148] HRMS: m / z (ESI) calculated [M+H] + : 365.0706, measured: 365.0719.

[0149] Example 8

[0150]

[0151] In a nitrogen-filled glove box, DMAP (0.04 mmol, 20 mol%), 4CzIPN (0.004 mmol, 2 mol%), NiBr2(dtbpy) (0.01 mmol, 5 mol%), HEH (0.5 mmol), K3PO4 (0.6 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and EA (3.0 mL) was added. Add 0.2 mmol of PPh₂Cl (0.22 mmol) and Cy₂NH₄⁺ (0.24 mmol) to the above mixture, and stir the mixture for 20 minutes on a magnetic stirrer set to 1000 rpm. Then add 0.2 mmol of iodine and (0.3 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0307 g of the target product. Its yield is 52%.

[0152] The above products were characterized as follows:

[0153] 1 H NMR (400 MHz, CDCl3) δ 7.41 (s, 1H), 7.37 (s, 1H), 5.35 (s, 2H), 3.54 - 3.50 (m, 2H), 3.03 (tt, J = 11.2 Hz, 3.6 Hz, 1H), 2.46 - 2.42 (m, 4H), 2.29 - 2.23 (m, 2H), 1.88 - 1.77 (m, 2H), 0.88 - 0.84 (m, 2H), -0.06 (s, 9H).

[0154] Example 9

[0155]

[0156] In a nitrogen-filled glove box, DMAP (0.04 mmol, 20 mol%), 4CzIPN (0.004 mmol, 2 mol%), NiBr2(dtbpy) (0.01 mmol, 5 mol%), HEH (0.5 mmol), K3PO4 (0.6 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and EA (3.0 mL) was added. Add 0.2 mmol of PPh₂Cl (0.22 mmol) and Cy₂NH₄⁺ (0.24 mmol) to the above mixture, and stir the mixture for 20 minutes on a magnetic stirrer set to 1000 rpm. Then add 0.2 mmol of iodine and (0.3 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0192 g of the target product. Its yield is 44%.

[0157] The above products were characterized as follows:

[0158] 1 H NMR (600 MHz, CDCl3) δ 8.57 - 8.56 (m, 1H), 8.18 (d, J = 1.8 Hz, 1H), 7.58 (td, J = 7.8 Hz, 1.8 Hz, 1H), 7.44 (dd, J = 8.4 Hz, 2.4 Hz, 1H),7.21 (d, J = 8.4 Hz, 1H), 7.15 - 7.13 (m, 1H), 7.05 (d, J = 7.2 Hz, 1H), 3.08(s, 4H);

[0159] 13 C NMR (151 MHz, CDCl3) δ 159.8, 149.7, 149.5, 149.1, 138.9, 136.5,135.7, 123.8, 123.1, 121.5, 39.4, 32.0;

[0160] HRMS: m / z (ESI) calculated [M+H] + : 219.0684, measured: 219.0692.

[0161] Example 10

[0162]

[0163] In a nitrogen-filled glove box, DMAP (0.04 mmol, 20 mol%), 4CzIPN (0.004 mmol, 2 mol%), NiBr2(dtbpy) (0.01 mmol, 5 mol%), HEH (0.5 mmol), K3PO4 (0.6 mmol), and 4ÅMS (100 mg) were placed into a 10 mL oven-dried Schlenk tube equipped with a magnetic stirrer, and EA (3.0 mL) was added. CD3OD (0.2 mmol), PPh2Cl (0.22 mmol), and Cy2NH (0.24 mmol) were added to the above mixture, and the mixture was stirred for 20 minutes at 1000 rpm with a magnetic stirrer. Then, elemental iodine (0.2 mmol) and (0.3 mmol). A sealed Schlenk tube was stirred at 1000 rpm with a magnetic stirrer and irradiated under blue light (λ = 450-455 nm) for 12 hours. The reaction mixture was quenched with water (3.0 mL), and the aqueous layer was extracted three times with ethyl acetate (2.0 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 0.0178 g of the target product. Its yield is 64%.

[0164] The above products were characterized as follows:

[0165] 1 H NMR (400 MHz, CDCl3) δ 6.71 - 6.60 (m, 3H), 5.90 (s, 2H);

[0166] 13 C NMR (101 MHz, CDCl3) δ 147.4, 145.3, 131.4, 121.5, 109.6, 108.0,100.6;

[0167] HRMS: m / z (ESI) calculated [2M+Na] + : 301.1317, measured: 301.1345.

[0168] Those skilled in the art should understand that variations can be implemented by combining existing technology with the above embodiments, which will not be elaborated here. Such variations do not affect the essence of the present invention, and will not be elaborated here either.

[0169] The preferred embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and the devices and structures not described in detail should be understood as being implemented in a conventional manner in the art. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the scope of the present invention. This does not affect the essential content of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the present invention's technical solutions still fall within the protection scope of the present invention.

Claims

1. A method for photocatalytic deoxyalkylation of alcohols, characterized in that: Under an inert gas atmosphere, an alcohol compound, a photocatalyst, a reducing agent, a condensing agent, diphenylchlorophosphine, a base, a molecular sieve, and an ultra-dry solvent are thoroughly mixed. An olefin and elemental iodine are then added sequentially, and the mixture is stirred under light irradiation to obtain an alcohol deoxyalkylation product. The light refers to visible light with a wavelength of 400-780 nm. The condensing agent is 4-dimethylaminopyridine. The photocatalyst consists of 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, terpyridine ruthenium chloride hexahydrate, and tri(2-(4-)pyridine. -trifluoromethylphenyl)pyridine)iridium, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate), 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile, 2,3,5,6-tetra(9-carbazolyl)-terephthalonitrile; the reducing agent is 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylic acid diethyl ester, zinc, manganese, magnesium, tetra(trimethylamino)ethylene or pinacol diborate.

2. The method for photocatalytic deoxyalkylation of alcohols according to claim 1, characterized in that, The inert gas refers to nitrogen, helium, or argon; thorough mixing means stirring for at least 20 minutes; the reaction time is 0.1 to 72 hours; the alcohols include primary alcohols, secondary alcohols, tertiary alcohols, or their isotopic substitutes. After the reaction, the reaction product is quenched, washed, extracted and dried, and then separated by a chromatography column to obtain the alcohol deoxyalkylated product.

3. The method for photocatalytic deoxyalkylation of alcohols according to claim 2, characterized in that, The alkali is one or more of the following: cesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium phosphate, dipotassium hydrogen phosphate, lithium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, lithium methoxide, sodium methoxide, potassium methoxide, sodium acetate, cesium acetate, cesium fluoride, triethylamine, trimethylamine, diisopropylamine, diisopropylmethylamine, dicyclohexylamine, dicyclohexylmethylamine, dimethylamine, diethylamine, dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethylethylenediamine, and tetramethylguanidine. The molecular sieve is a 3Å molecular sieve, a 4Å molecular sieve, or a 5Å molecular sieve. The ultra-dry solvent is one or more of the following: 1,4-dioxane, N,N'-dimethylacetamide, 1,2-dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, acetone, toluene, benzene, thylbenzene, xylene, ethyl acetate, methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, methyl formate, ethyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, benzyl formate, ethyl acetoacetate, diethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, 3-methylfuran, dioxolane, methyl tert-butyl ether, anisole, tetrahydropyran, N-methylpyrrolidone, and methylcyclopentyl ether. The reaction temperature is -40~80℃, and the time is 0.1~72h; The light is provided by 10-40W blue light, ultraviolet light or energy-saving lamp; The base is 10-600% molar equivalent of the alcohol compound; The reducing agent is 100-600% molar equivalent of the alcohol compound; The photocatalyst is 0.01% to 10% molar equivalent of the alcohol compound; The condensing agent is 5% to 20% molar equivalent of the alcohol compound; The molar ratio of the alcohol to the olefin is 1:5 to 5:1; The diphenylchlorophosphine is 100-600% molar equivalent of the alcohol compound; The molecular sieve is present in quantities of 0.1 to 1000 grams per mole; The elemental iodine is 10-300% molar equivalent of the alcohol compound; The concentration of the alcohol compound in the mixture is 0.0001~1 mol / L.

4. The method for photocatalytic deoxyalkylation of alcohols according to claim 3, characterized in that, The alkali is one or more of cesium carbonate and potassium phosphate; The molecular sieve is a 4Å molecular sieve; The ultra-dry solvent is ethylene glycol dimethyl ether; The reaction temperature is 15~30℃; The photocatalyst is 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile; The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate; The light is provided by a 30W blue light lamp; The base is 200-500% molar equivalent of the alcohol compound; The reducing agent is 150-300% molar equivalent of the alcohol compound; The photocatalyst is 1% to 2% molar equivalent of the alcohol compound; The molar ratio of the alcohol to the olefin is 1:3 to 2:1; The diphenylchlorophosphine is 110% molar equivalent of the alcohol compound; The molecular sieve is 500 grams per mole; The elemental iodine is 100% molar equivalent of the alcohol compound.

5. The method for photocatalytic deoxyalkylation of alcohols according to claim 1, characterized in that, The chemical formula of the olefin is shown in Formula I: In Formula I, R1 is a hydrogen atom or an aryl group, and R2 and R3 are independently selected from two of the following: hydrogen atom, halogen atom, alkyl acrylate, benzyl acrylate, aryl acrylate, acrylonitrile, acrolein, acrylone, sulfone, and propylene phosphate.

6. A method for photocatalytic deoxyarylation of alcohols, characterized in that: Under an inert gas atmosphere, an alcohol compound, a photocatalyst, a metal catalyst, a ligand, a reducing agent, a condensing agent, diphenylchlorophosphine, a base, a molecular sieve, and an ultra-dry solvent are thoroughly mixed. Then, aryl iodine and elemental iodine are added sequentially, and the mixture is stirred under light irradiation to obtain the alcohol deoxyarylated product. The light refers to visible light with a wavelength of 400-780 nm. The condensing agent is 4-dimethylaminopyridine. The photocatalyst consists of 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, terpyridineruthenium chloride hexahydrate, and tris(2-(4-trifluoromethylphenyl)pyridine)iridium. The metal catalysts are: bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium di(hexafluorophosphate), 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile (3DPAFIPN), and 2,3,5,6-tetra(9-carbazolyl)-terephthalonitrile; the metal catalysts are nickel dimethyl ether bromide, bis-(1,5-cyclooctadiene) nickel, nickel acetylacetonate, nickel dimethyl ether chloride, nickel bromide, nickel chloride, nickel iodide, nickel trifluoromethanesulfonate, palladium chloride, copper trifluoromethanesulfonate, or cobalt acetylacetonate; The ligands are 4,4'-di-tert-butyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 4,4'-diethylbisphosphate-2,2'-bipyridine, 2,2'-dimethyl-2,2'-bipyridine, 3,3'-dimethyl-2,2'-bipyridine, 2,2'-bipyridine, 1,10-o-phenanthroline, tripyridine, 4,7-dimethyl-1,10-o-phenanthroline, 4,7-diphenyl-1,10-o-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,2':6',2"-triphenyl-2,4'-dimethyl ... Bipyridine, 4,4',4''-tritert-butyl-2,2':6',2''-tribipyridine, 2,6-bis(1-pyrazolyl)pyridine, triphenylphosphine, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, bis(diphenylphosphine)ferrocene, (S)-4-isopropyl-2-(pyridin-2-yl)-4,5-dihydrooxazole, bis((S)-4-phenyl-4,5-dihydrooxazol-2-yl)methane or (S)-2-(2-(diphenylphosphine)phenyl)-4-isopropyl-4,5-dihydrooxazole; The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate, zinc, manganese, magnesium, tetra(dimethylamino)ethylene, or pinacol diboronate.

7. The method for photocatalytic deoxyarylation of alcohols according to claim 6, characterized in that, The inert gas refers to nitrogen, helium, or argon; thorough mixing means stirring for at least 20 minutes; the stirring reaction time is 0.1 to 72 hours; the alcohols include primary alcohols, secondary alcohols, tertiary alcohols, or their isotopic substitutes. After the reaction, the reaction product is quenched, washed, extracted and dried, and then separated by chromatography to obtain the alcohol deoxyarylated product.

8. The method for photocatalytic deoxyarylation of alcohols according to claim 7, characterized in that, The alkali is one or more of the following: cesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium phosphate, dipotassium hydrogen phosphate, lithium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, lithium methoxide, sodium methoxide, potassium methoxide, sodium acetate, cesium acetate, cesium fluoride, triethylamine, trimethylamine, diisopropylamine, diisopropylmethylamine, dicyclohexylamine, dicyclohexylmethylamine, dimethylamine, diethylamine, dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethylethylenediamine, and tetramethylguanidine. The molecular sieve is a 3Å molecular sieve, a 4Å molecular sieve, or a 5Å molecular sieve. The ultra-dry solvent is one or more of the following: 1,4-dioxane, N,N'-dimethylacetamide, 1,2-dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, acetone, toluene, benzene, thylbenzene, xylene, ethyl acetate, methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, methyl formate, ethyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, benzyl formate, ethyl acetoacetate, diethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, 3-methylfuran, dioxolane, methyl tert-butyl ether, anisole, tetrahydropyran, N-methylpyrrolidone, and methylcyclopentyl ether. The reaction temperature is -40~80℃, and the time is 0.1~72h; The light is provided by 10-40W blue light, ultraviolet light or energy-saving lamp; The base is 10-600% molar equivalent of the alcohol compound; The reducing agent is 100-600% molar equivalent of the alcohol compound; The photocatalyst is 0.01% to 10% molar equivalent of the alcohol compound; The condensing agent is 5% to 20% molar equivalent of the alcohol compound; The metal catalyst is 0.01% to 100% molar equivalent of the alcohol compound; The ligand is 0.012% to 120% molar equivalent of the alcohol compound; The molar ratio of the alcohol compound to the aryl iodine is 1:5 to 5:1; The diphenylchlorophosphine is 100-600% molar equivalent of the alcohol compound; The molecular sieve is present in quantities of 0.1 to 1000 grams per mole; The elemental iodine is 10-300% molar equivalent of the alcohol compound; The concentration of the alcohol compound in the mixture is 0.0001~1 mol / L.

9. The method for photocatalytic deoxyarylation of alcohols according to claim 8, characterized in that, The alkali is potassium phosphate; The molecular sieve is a 4Å molecular sieve; The ultra-dry solvent is ethyl acetate; The reaction temperature is 15~30℃; The photocatalyst is 4,5,6-tetra(9-carbazolyl)-isophthalonitrile; The metal catalyst is nickel ethylene glycol dimethyl ether bromide; The ligand is 4,4'-di-tert-butyl-2,2'-bipyridine; The reducing agent is diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate; The light is provided by a 30W blue light lamp; The base is 300% molar equivalent of the alcohol compound; The reducing agent is 250% molar equivalent of the alcohol compound; The photocatalyst is 1% to 2% molar equivalent of the alcohol compound; The metal catalyst is 5% molar equivalent of the alcohol compound; The ligand is 6% molar equivalent of the alcohol compound; The molar ratio of the alcohol compound to the aryl iodine is 1:1.5; The diphenylchlorophosphine is 110% molar equivalent of the alcohol compound; The molecular sieve is 500 grams per mole; The elemental iodine is 100% molar equivalent of the alcohol compound.

10. The method for photocatalytic deoxyarylation of alcohols according to claim 6, characterized in that, The chemical formula of the aryl iodine is shown in Formula II or Formula III: In Formula II, R1 is a methyl, methoxy, cyano, aldehyde, ester, ketone, trifluoromethyl, or halogen atom; In Formula III, R1, R2, R4, and R5 are independently selected from one of the following: methoxy group, ester group, fluorine atom, chlorine atom, bromine atom, and hydrogen atom, and R3 is (trimethylsilyl)ethoxymethyl.

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