Carboxylate compound reduction method

Abstract

The invention provides a reduction method of a carboxylic ester compound. The method comprises the following steps: in a solvent, under the conditions of a phenol catalyst, alkali, an additive and illumination, carrying out a reduction reaction on a compound containing a fragment I and a hydrogen source to obtain a compound containing a fragment II. The preparation method disclosed by the invention is high in yield, few in by-products, wide in substrate application range, good in functional group compatibility and mild in reaction condition.

Description

Technical Field

[0001] The invention relates to a reduction method of carboxylic acid ester compounds. Background Art

[0002] Carboxylic acid ester compounds (molecular formula R-COO-R') are highly abundant in nature and are a potential biomass platform molecule. This structural unit is widely present in various natural products, drugs, materials and chemical raw materials. Due to its easy availability, easy conversion and stability, ester groups are used in various functional group conversion reactions during chemical synthesis and are often used as precursors for other functional groups such as carboxylic acids, amides, alcohols, aldehydes, etc.

[0003] The reduction of carboxylic acid ester groups to alcohols and aldehydes is the most basic and important functional group conversion reaction in organic chemical synthesis. Alcohol and aldehyde compounds are widely present in drug molecules and fine chemical products, and are widely used synthetic building blocks in organic synthesis. The reduction of carboxylic acid ester groups to alcohols or aldehydes generally includes catalytic hydrogenation, metallic sodium reduction, and metal hydride negative hydrogen transfer reduction (including aluminum hydride, borohydride). Catalytic hydrogenation reduction of carboxylic acid esters usually requires heavy metal catalysts (such as palladium, ruthenium, nickel, etc.) under high temperature and high pressure reaction conditions, as well as the use of flammable and explosive hydrogen, which poses serious safety risks in production. This reduction method not only has harsh conditions and high equipment requirements, but also catalytic hydrogenation will reduce other functional groups such as double bonds, and the presence of heavy metal residues limits its application in drug synthesis. The metallic sodium reduction method is inconvenient to use in industrialization because alkali metals are sensitive to water, air, etc. and are easily flammable. The reduction of carboxylates to alcohols by metal hydrides is currently the most commonly used method in laboratories and industries. The commonly used reagents in laboratories are lithium aluminum hydride and potassium borohydride. The main limitations are that they decompose and spontaneously combust when wet, which can easily cause fires. They have poor solubility and are limited to solvents that can be processed into absolutely dry solvents. Industrial production is very dangerous. The high price of metal hydrides, large amounts of solvents, and high processing costs lead to high costs of use.

[0004] In addition, the current method of preparing deuterated or tritiated aldehyde and alcohol products by reducing carboxylic acid ester compounds requires the use of expensive aluminum deuterium or tritium, which makes it difficult to achieve industrial-scale mass production. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the harsh reaction conditions of the reduction method of carboxylic acid ester compounds in the prior art, and provide a reduction method of carboxylic acid ester compounds. Under the action of phenol catalyst, alkali, hydrogen source and light, the graded reduction of carboxylic acid ester compounds can be achieved to obtain alcohol compounds. When there is an additive in the reaction system, aldehyde compounds can be obtained. In addition, if a deuterated or tritiated reagent is added to the reaction system, the hydrogen source reagent first undergoes an exchange reaction with the deuterated or tritiated reagent, and the deuterated or tritiated hydrogen source reagent is obtained to participate in the subsequent reaction, and the corresponding deuterated or tritiated aldehyde and alcohol compounds can be prepared. The preparation method of the present application has high product yield, few by-products, a wide range of substrate applications, good functional group compatibility, and mild reaction conditions.

[0006] The present invention provides a method for preparing an aldehyde compound, which comprises the following steps: in a solvent, under the conditions of a phenol catalyst, a base, an additive and light, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment II;

[0007] Wherein, the fragment I is

[0008] The fragment II is

[0009] The phenol catalyst is

[0010] Ring A is C 6-14 Aryl or 5-10 membered heteroaryl; the heteroatom in the 5-10 membered heteroaryl is selected from one or more of N, O and S, and the number of heteroatoms is 1-4;

[0011] R 1 Each independently is H, C 1-10 Alkyl, -OR 1a 、-NO2、-(C=O)R 1b 、-NR 1c R 1d , C 6-14 Aryl, 5-10 membered heteroaryl, substituted by one or more R 1e Substituted C 1-10 Alkyl, with one or more R 1f Substituted C 6-14 Aryl, or one or more R 1g substituted 5-10 membered heteroaryl; the 5-10 membered heteroaryl and one or more R 1g The heteroatom in the substituted 5-10 membered heteroaryl is selected from one or more of N, O and S, and the number of the heteroatoms is 1-4;

[0012] m is 1, 2, 3, 4 or 5;

[0013] R 1a and R 1b Each independently is H or C 1-10 alkyl;

[0014] R 1c and R 1d Each independently is H, C 6-14 Aryl, or substituted by one or more R 1a-1 C 6-14 Aryl;

[0015] R 1e , R 1f and R 1g Each independently is -OH, C 1-10 Alkyl, NR 1a-2 R 1a-3 、-(C=O)R 1a-4 or -CN;

[0016] R 1a-1 , R 1a-2 , R 1a-3 or R 1a-4 independently H or C 1-10 alkyl;

[0017] The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment II;

[0018] The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene group in the fragment I is directly connected; the carbonyl group in the fragment I is not connected to N, O and S.

[0019] In the present invention, the additive refers to an additive that can react with an aldehyde group to generate an enamine or a half-amine acetal intermediate. After the reaction is terminated, the generated enamine or half-amine acetal intermediate is re-hydrolyzed in a post-treatment process to obtain an aldehyde compound.

[0020] In the preparation method of the aldehyde compound, the solvent may be a conventional solvent for such reactions in the art. Preferably, the solvent is one or more of an alkane solvent, an aromatic solvent, an ether solvent, a nitrile solvent, an alcohol solvent, an amide solvent, a sulfoxide solvent, water and pyridine. The alkane solvent is preferably n-hexane, cyclohexane, heptane, n-pentane, petroleum ether or gasoline, more preferably n-hexane, cyclohexane or petroleum ether. The aromatic solvent is preferably benzene, toluene, xylene or trimethylbenzene, more preferably benzene or toluene. The ether solvent is preferably tetrahydrofuran, ether, isopropyl ether, 1,4-dioxane or methyl tert-butyl ether, more preferably tetrahydrofuran, ether, 1,4-dioxane or methyl tert-butyl ether. The nitrile solvent is preferably acetonitrile. The alcohol solvent is preferably methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol or tert-butanol, more preferably methanol, ethanol, isopropanol or tert-butanol. The amide solvent is preferably N,N-dimethylformamide or N,N-dimethylacetamide, more preferably N,N-dimethylformamide. The sulfoxide solvent is preferably dimethyl sulfoxide.

[0021] In the method for preparing the aldehyde compound, the solvent is preferably a mixed solvent of an ether solvent and water, such as tetrahydrofuran and water (the volume ratio of tetrahydrofuran to water is preferably 9:1).

[0022] In the method for preparing the aldehyde compound, the amount of the solvent may not be specifically limited, as long as it does not affect the reaction. The concentration of the compound containing fragment I in the solvent may be a conventional concentration for such reactions in the art, preferably 0.05-0.75 mol / L, such as 0.06 mol / L, 0.075 mol / L, 0.10 mol / L, 0.15 mol / L or 0.30 mol / L.

[0023] In the method for preparing the aldehyde compound, the molar ratio of the phenol catalyst to the compound containing fragment I is preferably (0.005-0.2):1, more preferably (0.01-0.15):1, for example 0.02:1, 0.05:1, 0.07:1, 0.09:1 or 0.10:1.

[0024] In the preparation method of the aldehyde compound, the base is preferably sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, ammonium carbonate, triethylmethyl methyl ammonium carbonate (CAS: 113840-08-7), tributylmethyl methyl ammonium carbonate (CAS: 274257-37-3), potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tributylbenzylammonium hydroxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, 2,4,6-trimethylpyridine, 4-dimethylamino The alkyl pyridine, triethylamine, trimethylamine, diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetramethylguanidine, tetramethylethylenediamine, N-methylmorpholine, N,N,N',N",N"-pentamethyldiethylenetriamine or phosphazene base (CAS: 111324-04-0), more preferably lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, ammonium carbonate, cesium hydroxide, ammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, tetramethylguanidine, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, potassium tert-butoxide, potassium methoxide, DBU, 2,6-di-tert-butylpyridine or diisopropylethylamine.

[0025] In the method for preparing the aldehyde compound, the molar ratio of the base to the compound containing fragment I is preferably (0.2-5):1, more preferably (2-3):1, for example 2.7:1.

[0026] In the preparation method of the aldehyde compound, preferably, the additive is Among them, R A1 and R A2 Independently for C 1-4 alkyl;

[0027] R A3 H, C 1-4 Alkyl, -C 1-4 Alkylene -OH or -C 1-4 Alkylene -NH2;

[0028] X 1 is -CH2-, -O- or -NH-;

[0029] n is 0, 1 or 2.

[0030] In the method for preparing the aldehyde compound, the molar ratio of the additive to the compound containing fragment I is preferably (1-5):1, for example 2:1.

[0031] In the method for preparing the aldehyde compound, preferably, the hydrogen source is R B1 -SH, HCO2H, H2S, alkali metal sulfides, dihydrogenated C 6-14 Aryl, dihydrogenated 5-10 membered heteroaryl, B3 Substituted dihydrogenated C 6-14 Aryl, or one or more R B4 substituted dihydrogenated 5-10 membered heteroaryl; said dihydrogenated 5-10 membered heteroaryl and substituted by one or more R B4 The heteroatom in the substituted dihydrogenated 5-10 membered heteroaryl is selected from one or more of N, O and S, and the number of the heteroatoms is 1-4;

[0032] Among them, R B1 C 1-4 Alkyl, C 3-10 Cycloalkyl, -C 1-4 Alkylene-CO2H, (C 1-4 Alkyl)3Si-, C 6-14 Aryl, or one or more R B1-1 Substituted C 6-14 Aryl;

[0033] R B2 C 1-4 Alkyl, C 3-10 Cycloalkyl, (C 1-4 Alkyl)3Si-, C 6-14 Aryl, or one or more R B2-1 Substituted C 6-14 Aryl;

[0034] R B1-1 and R B2-1 Each independently is C 1-4 alkyl;

[0035] R B3 and R B4 Each independently is C 1-4 Alkyl or -CH2Ph;

[0036] and are independently alkali metal ions (such as Li + 、Na + , K + or Cs + ) or NH4 + .

[0037] In the present invention, the dihydrogenated C 6-14 Aryl refers to C 6-14 A group in which one double bond in an aromatic group is reduced to a single bond.

[0038] In the present invention, the dihydrogenated 5-10 membered heteroaryl group refers to a group in which one double bond in the 5-10 membered heteroaryl group is reduced to a single bond.

[0039] In the method for preparing the aldehyde compound, the molar ratio of the amount of the hydrogen source to the compound containing fragment I is preferably (1.0-6.0):1, more preferably (1.0-3.0):1, for example 1.1:1, 1.2:1, 1.3:1, 1.5:1, 1.7:1, 2.0:1 or 2.3:1.

[0040] In the method for preparing aldehyde compounds, the light source of the illumination is preferably an LED lamp, an incandescent lamp or an energy-saving lamp (such as a white energy-saving lamp). The power of the LED lamp is preferably 2-10 watts, such as 5-8 watts. The power of the incandescent lamp is preferably 20 watts. The power of the energy-saving lamp is preferably 20 watts.

[0041] In the method for preparing aldehyde compounds, the light source is preferably 3-8 cm away from the reaction device, such as 5-6 cm.

[0042] In the method for preparing the aldehyde compound, the wavelength of the illumination may be a single wavelength or a mixed wavelength. The single wavelength may be in the visible light range, preferably 390-600 nm, more preferably 395-515 nm, such as 400 nm, 405 nm, 410 nm, 415 nm, 435 nm, 450 nm, 455 nm, 470 nm or 475 nm. The mixed wavelength is preferably in the range of 400 nm-550 nm.

[0043] In the preparation method of the aldehyde compound, the reaction temperature of the reduction reaction can be a conventional temperature for such reactions in the art, preferably -20°C-80°C, more preferably -10°C-50°C, for example 0°C, 15°C, 25°C, 22°C, 35°C, 40°C or 45°C.

[0044] In the method for preparing the aldehyde compound, the progress of the reduction reaction can be monitored by conventional detection methods in the art (e.g., TLC, HPLC, HNMR), and preferably the disappearance or no-reaction of the compound containing fragment I is used as the end point of the reaction. The reaction time of the reduction reaction can be 6-40 hours, preferably 8-28 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 15 hours, 16 hours, 18 hours, 20 hours or 26 hours.

[0045] In the preparation method of the aldehyde compound, the reduction reaction preferably further comprises the following post-treatment steps: adding water to the reaction solution to quench the reaction, extracting with an organic solvent (such as ethyl acetate), washing with water and saturated sodium chloride solution in sequence, drying (preferably drying with anhydrous sodium sulfate), concentrating and then column chromatography.

[0046] In one embodiment of the present invention, some groups are defined as follows, and undefined groups are the same as described above (hereinafter referred to as "in one embodiment"):

[0047] In one embodiment, ring A, R 1 , R 1c , R 1d , R B1 and R B2 In the C 6-14 Aryl, one or more R 1f Substituted C 6-14 Aryl, substituted by one or more R 1a-1 C 6-14 Aryl, one or more R B1-1 Substituted C 6-14 Aryl and one or more R B2-1 Substituted C 6-14 C in aromatic groups 6-14 Aryl is phenyl, naphthyl, anthracenyl, phenanthryl or fluorenyl.

[0048] In one embodiment, the dihydrogenated C 6-14 Aryl and one or more R B3 Substituted dihydrogenated C 6-14 C in aromatic groups 6-14 Aryl is phenyl, naphthyl, anthracenyl, phenanthryl or fluorenyl.

[0049] In one embodiment, ring A and R 1 wherein the 5-10 membered heteroaryl group and one or more R 1g The 5- to 10-membered heteroaryl in the substituted 5- to 10-membered heteroaryl is preferably a pyridyl or indolyl group (e.g.

[0050] In one embodiment, the dihydrogenated 5-10 membered heteroaryl and one or more R B4 The 5-10 membered heteroaryl in the substituted dihydrogenated 5-10 membered heteroaryl is preferably pyridyl, quinolyl, isoquinolyl, indolyl, pyrrolyl, pyrazinyl, pyrimidinyl, furyl, benzofuranyl, benzothiazolyl, benzothienyl or carbazolyl, more preferably pyrrolyl or indolyl.

[0051] In one scenario, R 1 , R 1a , R 1b , R1e , R 1f , R 1g , R 1a-1 , R 1a-2 , R 1a-3 and R 1a-4 In the C 1-10 Alkyl and one or more R 1e Substituted C 1-10 C in the alkyl group 1-10 Alkyl is C 1-4 Alkyl or C 6-10 Alkyl. 1-4 The alkyl group is preferably methyl, ethyl or tert-butyl. 6-10 The alkyl group is preferably n-heptyl.

[0052] In one scenario, R A1 , R A2 , R A3 , R B1 , R B2 , R B1-1 , R B2-1 , R B3 and R B4 In the C 1-4 Alkyl and (C 1-4 Alkyl)3Si-C 1-4 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl, ethyl, isopropyl, n-butyl or tert-butyl.

[0053] In one scenario, R A3 and R B1 In the -C 1-4 Alkylene -OH, -C 1-4 Alkylene -NH2 and -C 1-4 C in alkylene-CO2H 1-4 The alkylene group is methylene, -CH2CH2-, -CH(CH3)- or -CH2CH2CH2-, preferably methylene.

[0054] In one scenario, R B1 and R B2 In the C 3-10 Cycloalkyl is C 3-6 Cycloalkyl, for example cyclohexyl.

[0055] In the preparation method of the aldehyde compound, the phenol catalyst is any of the following compounds:

[0056]

[0057]

[0058] In the method for preparing the aldehyde compound, the additive is preferably prolinol, tetrahydropyrrole, morpholine, dimethylamine or piperidine. In the method for preparing the aldehyde compound, in the hydrogen source, R B1 -SH is thiophenol, p-methylthiophenol, cyclohexyl mercaptan, ethyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, thioglycolic acid, cysteine ​​or triisopropylsilanethiol. Preferably, it is cesium formate, potassium formate, sodium formate or ammonium formate. The alkali metal sulfide is preferably sodium sulfide. The dihydrogenated C 6-14 The aryl group is preferably 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,2-dihydronaphthalene or 9,10-dihydrophenanthrene. The dihydrogenated 5-10 membered heteroaryl group is preferably indoline or 3-dihydropyrrole. B4 The substituted dihydrogenated 5- to 10-membered heteroaryl group is preferably 2-methyl-2-imidazoline or 2-benzyl-2-imidazoline.

[0059] In a certain embodiment, the preparation method of the aldehyde compound is the following method 1, method 2 or method 3;

[0060] Method 1: In a solvent, under the conditions of a phenol catalyst, a base, an additive and light, a compound represented by Formula IA and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula II-A;

[0061]

[0062] Method 2: In a solvent, under the conditions of a phenol catalyst, a base, an additive and light, a compound represented by Formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula II-B;

[0063]

[0064] Method 3: In a solvent, under the conditions of a phenol catalyst, a base, an additive and light, a compound represented by Formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula II-C;

[0065]

[0066] In method 1, method 2 and method 3, the solvent, phenol catalyst, base, additive and light conditions are as described in any of the previous items;

[0067] Among them, R 2 For-LR 2a , C 1-10 Alkyl, C 3-20 Cycloalkyl, C 6-14 Aryl, 5-10 membered heteroaryl, C 3-25Cycloalkenyl, 3-25 membered heterocyclic group, 2b Substituted C 1-10 Alkyl, with one or more R 2c Substituted C 3-20 Cycloalkyl, with one or more R 2d Substituted C 6-14 Aryl, one or more R 2e substituted 5-10 membered heteroaryl, substituted by one or more R 2f Substituted C 3-25 Cycloalkenyl, or one or more R 2g substituted 3-25 membered heterocyclyl;

[0068] L is -C 1-10 Alkylene-C(R 2a-1 R 2a-2 )-;

[0069] R 2a C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-14 Aryl, or one or more R 2a-3 Substituted C 6-14 Aryl;

[0070] R 2a-1 and R 2a-2 Independently H, C 1-4 Alkyl or -NH2;

[0071] R 2a-3 C 1-4 Alkyl or C 1-4 Alkoxy;

[0072] R 2b -OH, -CN, -N(R 2b-3 R 2b-4 ), 5-10 membered heteroaryl, 3-25 membered heterocyclic group, C 3-20 Cycloalkyl, with one or more R 2b-5 Substituted C 3-20 Cycloalkyl, or one or more R 2b-6 substituted 3-25 membered heterocyclyl;

[0073] R 2b-1 and R 2b-2 Independently for C 1-4 alkyl;

[0074] R 2b-3 and R 2b-4 Independently H, C 1-4 Alkyl or And R 2b-3 and R2b-4 Not at the same time H;

[0075] R 2b-5 and R 2b-6 are independently -OH, C 1-4 Alkyl or oxo (=O);

[0076] R 2c , R 2d , R 2e , R 2f and R 2g are independently halogen, -OH, oxo (=O), C 1-4 Alkyl, C 1-4 Alkoxy, -N(R 2d- 1 R 2d-2 ), or C substituted by one or more hydroxyl groups 1-4 alkyl;

[0077] R 2d-1 and R 2d-2 Independently H, C 1-4 Alkyl, -(C=O)C 1-4 Alkyl or -(C=O)OC 1-4 alkyl;

[0078] The 5-10 membered heteroaryl, 3-25 membered heterocyclic group, 2e substituted 5-10 membered heteroaryl, substituted by one or more R 2g substituted 3-25 membered heterocyclic group and one or more R 2b-6 The heteroatom or heteroatom group in the substituted 3-25 membered heterocyclic group is selected from N, O, S and -(NR 7 )-, the number of heteroatoms is 1-4;

[0079] R 7 H or -(C=O)OC 1-4 alkyl;

[0080] R 3 , R 5 and R 6 Independently for C 1-10 Alkyl, C 3-20 Cycloalkyl, C 6-14 Aryl, one or more R 3a Substituted C 1-10 Alkyl or

[0081] R 3a each independently is -OH;

[0082] R 4 For -C3-20 Cycloalkyl-;

[0083] Ring B is C 3-20 Cycloalkyl, C 6-14 Aryl, one or more R C1 Substituted C 3-20 Cycloalkyl, or one or more R C2 Substituted C 6-14 Aryl;

[0084] R C1 and R C2 Independently for C 1-4 alkyl;

[0085] p is 1, 2 or 3.

[0086] In one scenario, R 2 , R 3 , R 5 and R 6 In the C 1-10 Alkyl, with one or more R 2b Substituted C 1-10 Alkyl and one or more R 3a Substituted C 1-10 C in the alkyl group 1-10 The alkyl groups are independently C 1-4 Alkyl or C 6-10 Alkyl. 1-4 The alkyl group is preferably methyl, ethyl, n-propyl, n-butyl or tert-butyl. 6-10 The alkyl group is preferably

[0087] In one scenario, R 2 , R 2b , R 3 , R 5 and R 6 In the C 3-20 Cycloalkyl, with one or more R 2c Substituted C 3-20 Cycloalkyl and one or more R 2b-5 Substituted C 3-20 C in cycloalkyl 3-20 The cycloalkyl groups are independently C 3-8 Cycloalkyl or C 10-20 Cycloalkyl. 3-8 The cycloalkyl group is preferably a cyclobutyl group or a cyclohexyl group. 10-20 The cycloalkyl group is preferably

[0088] In one embodiment, in ring B, the C 3-20 Cycloalkyl and one or more RC1 Substituted C 3-20 C in cycloalkyl 3-20 The cycloalkyl groups are independently C 6-10 Cycloalkyl, preferably

[0089] In one scenario, R 2 , R 2a , R 3 , R 5 and R 6 In the C 6-14 Aryl, one or more R 2d Substituted C 6-14 Aryl and one or more R 2a-3 Substituted C 6-14 C in aromatic groups 6-14 Aryl is independently phenyl, naphthyl or anthracenyl.

[0090] In one embodiment, in ring B, the C 6-14 Aryl and one or more R C2 Substituted C 6-14 C in aromatic groups 6-14 Aryl is independently phenyl.

[0091] In one scenario, R 2 and R 2b wherein the 5-10 membered heteroaryl and one or more R 2e The 5- to 10-membered heteroaryl in the substituted 5- to 10-membered heteroaryl is independently pyrrolyl, pyridyl or indolyl.

[0092] In one scenario, R 2 In the C 3-25 Cycloalkenyl and one or more R 2f Substituted C 3-25 C in cycloalkenyl 3-25 The cycloalkenyl groups are independently C 10-25 Cycloalkenyl, preferably

[0093] In one scenario, R 2 and R b wherein the 3-25 membered heterocyclic group is replaced by one or more R 2g substituted 3-25 membered heterocyclic group and one or more R 2b-6 The 3-25-membered heterocyclic group in the substituted 3-25-membered heterocyclic group is independently a 5-10-membered heterocyclic group and a 15-25-membered heterocyclic group. The 5-10-membered heterocyclic group is preferably a tetrahydropyrrolyl group (e.g. ), piperidinyl (e.g. ), pyranyl (e.g. The 15-25 membered heterocyclic group is preferably

[0094] In one embodiment, in L, the -C 1-10 Alkylene-C(R 2a-1 R 2a-2 )-C 1-10 Alkylene is methylene,

[0095]

[0096] In one scenario, R 2a In the C 2-20 Alkenyl is C 8-12 Alkenyl, e.g.

[0097] In one scenario, R 2a In the C 2-20 Alkynyl is C 2-6 Alkynyl, for example ethynyl.

[0098] In one scenario, R 2a-1 , R 2a-2 , R 2a-3 , R 2b-1 , R 2b-2 , R 2b-3 , R 2b-4 , R 2b-5 , R 2b-6 , R 2c , R 2d , R 2e , R 2f , R 2g , R 2d-1 , R 2d-2 , R 7 , R C1 and R C2 In the C 1-4 Alkyl, -(C=O)C 1-4 Alkyl, -(C=O)OC 1-4 Alkyl and C substituted by one or more hydroxyl groups 1-4 C in the alkyl group 1-4 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0099] In one scenario, R 2c , R 2d , R 2e , R 2f and R 2g In the above, the halogen is independently fluorine, chlorine, bromine or iodine, for example fluorine.

[0100] In one scenario, R 2a-3 , R 2c , R 2d , R 2e , R 2f and R 2g In the C 1-4 Alkoxy is independently methoxy.

[0101] In one scenario, R 4 In the -C 3-20 Cycloalkyl- is -C 5-10 Cycloalkyl-, e.g.

[0102] In one embodiment, the R 2 for

[0103]

[0104] In one scenario, R 3 Methyl, ethyl, tert-butyl, Phenyl, cyclohexyl or

[0105]

[0106] In one scenario, R 4 for

[0107] In one scenario, R 5 and R 6 are independently methyl.

[0108] In one embodiment, ring B is In one embodiment, the compound shown in IA is selected from any of the following compounds:

[0109]

[0110] In one embodiment, the compound shown in IB is In a certain embodiment, the compound shown in the IC is selected from any of the following compounds:

[0111] In the method for preparing the aldehyde compound, the reagents for the reduction reaction are preferably the solvent, the phenol catalyst, the base, the additive, the compound containing fragment I (for example, the compound represented by formula IA, IB or IC) and a hydrogen source.

[0112] In the method for preparing the aldehyde compound, the reagent for the reduction reaction does not contain a deuterated reagent or a tritiated reagent.

[0113] The present invention provides a method for preparing a deuterated or tritiated aldehyde compound, which comprises the following steps: in an aprotic solvent, under the conditions of a phenol catalyst, a base, an additive and light, 2 H) reagent or tritiated ( 3 H) reducing the compound containing fragment I with a hydrogen source in the presence of a reagent to obtain a compound containing fragment III;

[0114] Wherein, the fragment I is

[0115] The fragment III is

[0116] The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment III;

[0117] The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene in the fragment I is directly connected; the carbonyl in the fragment I is not connected to N, O and S;

[0118] The phenol catalyst, base, additive, light and hydrogen source are as described above, and the reaction temperature and reaction time of the reduction reaction are as described above.

[0119] In the method for preparing the deuterated aldehyde compound, the reagents for the reduction reaction are preferably the aprotic solvent, a phenol catalyst, a base, an additive, a compound containing fragment I (for example, a compound represented by formula IA, IB or IC), a hydrogen source and a deuterated reagent.

[0120] In the method for preparing the tritiated aldehyde compound, the reagents for the reduction reaction are preferably the aprotic solvent, a phenol catalyst, a base, an additive, a compound containing fragment I (for example, a compound represented by formula IA, IB or IC), a hydrogen source and a tritiated reagent.

[0121] In the preparation method of the deuterated or tritiated aldehyde compound, in the presence of a deuterated reagent, the fragment III is

[0122] In the method for preparing the deuterated or tritiated aldehyde compound, in the presence of a tritiated reagent, the fragment III is

[0123] In the preparation method of the deuterated or tritiated aldehyde compound, the aprotic solvent is preferably one or more of an alkane solvent, an aromatic solvent, an ether solvent, a nitrile solvent and a sulfoxide solvent, and is more preferably an ether solvent. The alkane solvent is preferably n-hexane, cyclohexane, heptane, n-pentane, petroleum ether or gasoline. The aromatic solvent is preferably benzene, toluene, xylene or trimethylbenzene. The ether solvent is preferably tetrahydrofuran, diethyl ether, isopropyl ether, 1,4-dioxane or methyl tert-butyl ether. The nitrile solvent is preferably acetonitrile. The sulfoxide solvent is preferably dimethyl sulfoxide.

[0124] In the method for preparing the deuterated or tritiated aldehyde compound, the deuterated reagent is preferably deuterated water, R 8 -O 2 H or R 8 and R 9 Independently for C 1-4 Alkyl or C 6-14 More preferably, the deuterated reagent is deuterated water, MeO 2 H, EtO 2 H、iPrO 2 H or MeCO2 2 H.

[0125] In the method for preparing the deuterated or tritiated aldehyde compound, the molar ratio of the deuterated reagent to the compound containing fragment I is preferably (10-30):1, for example 20:1.

[0126] In the method for preparing the deuterated or tritiated aldehyde compound, the tritiated reagent is preferably tritiated water, R 10 -O 3 H or R 10 and R 11 Independently for C 1-4 Alkyl or C 6-14 More preferably, the tritiated reagent is tritiated water.

[0127] In the method for preparing the deuterated or tritiated aldehyde compound, the molar ratio of the amount of the tritiated reagent to the compound containing fragment I is preferably (10-30):1, for example 20:1.

[0128] In a certain embodiment, the preparation method of the deuterated or tritium aldehyde compound is the following method 1, method 2 or method 3;

[0129] Method 1: In an aprotic solvent, in the presence of a phenol catalyst, a base, an additive and light, a compound as shown in Formula IA and a hydrogen source are subjected to a reduction reaction in the presence of a deuterated reagent or a tritium reagent to obtain a compound as shown in Formula III-A;

[0130]

[0131] Method 2: In an aprotic solvent, in the presence of a phenol catalyst, a base, an additive and light, in the presence of a deuterated reagent or a tritium reagent, a compound as shown in Formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula III-B;

[0132]

[0133] Method 3: In an aprotic solvent, in the presence of a phenol catalyst, a base, an additive and light, in the presence of a deuterated reagent or a tritium reagent, a compound as shown in Formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula III-C;

[0134]

[0135] In method 1, method 2 and method 3, the aprotic solvent, phenol catalyst, base, additive, light, hydrogen source, the compound shown in formula IA, the compound shown in formula IB, the compound shown in formula IC, the deuterated reagent and the tritiated reagent are as described above, and the reaction temperature and reaction time of the reduction reaction are as described above.

[0136] The present invention provides a method for preparing an alcohol compound, which comprises the following steps: in a solvent, under the conditions of a phenol catalyst, an alkali and light, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment IV;

[0137] Wherein, the fragment I is

[0138] The fragment IV is

[0139] The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment IV;

[0140] The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene in the fragment I is directly connected; the carbonyl in the fragment I is not connected to N, O and S;

[0141] The solvent, phenol catalyst, base, light and hydrogen source are as described above.

[0142] In the method for preparing the alcohol compound, the reagents for the reduction reaction are preferably the solvent, the phenol catalyst, a base, a compound containing fragment I (for example, a compound represented by formula IA, IB or IC) and a hydrogen source.

[0143] In the method for preparing the aldehyde compound, the reagent for the reduction reaction does not contain additives, deuterated reagents and tritiated reagents.

[0144] In a certain embodiment, the preparation method of the alcohol compound is the following method 1, method 2 or method 3;

[0145] Method 1: In a solvent, under the conditions of phenol catalyst, base and light, a compound as shown in formula IA and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in formula IV-A;

[0146]

[0147] Method 2: In a solvent, under the conditions of phenol catalyst, base and light, the compound represented by formula IB and a hydrogen source are subjected to reduction reaction to obtain a compound represented by formula IV-B;

[0148]

[0149] Method 3: In a solvent, under the conditions of phenol catalyst, base and light, the compound represented by formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by formula IV-C;

[0150]

[0151] The solvent, phenol catalyst, base, light, hydrogen source, compound of formula IA, compound of formula IB, and compound of formula IC are as described above; the temperature and reaction time of the reduction reaction are as described above.

[0152] The present invention provides a method for preparing a deuterated or tritiated alcohol compound, which comprises the following steps: in an aprotic solvent, under the conditions of a phenol catalyst, a base and light, in the presence of a deuterated reagent or a tritiated reagent, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment V;

[0153] Wherein, the fragment I is

[0154] The fragment V is

[0155] The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment V;

[0156] The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene in the fragment I is directly connected; the carbonyl in the fragment I is not connected to N, O and S;

[0157] The aprotic solvent, phenol catalyst, base, light, hydrogen source, deuterated reagent and tritium reagent are as described above.

[0158] In the method for preparing the deuterated alcohol compound, the reagents for the reduction reaction are preferably the aprotic solvent, a phenol catalyst, a base, a compound containing fragment I (for example, a compound represented by formula IA, IB or IC), a hydrogen source and a deuterated reagent.

[0159] In the method for preparing the tritiated alcohol compound, the reagents for the reduction reaction are preferably the aprotic solvent, a phenol catalyst, a base, a compound containing fragment I (for example, a compound represented by formula IA, IB or IC), a hydrogen source and a tritiated reagent.

[0160] In the method for preparing the deuterated or tritiated alcohol compound, the reagent for the reduction reaction does not contain additives.

[0161] In the preparation method of the deuterated or tritiated alcohol compound, in the presence of a deuterated reagent, the fragment V is In the presence of a tritiated reagent, the fragment V is

[0162] In a certain embodiment, the preparation method of the deuterated or tritiated alcohol compound is the following method 1, method 2 or method 3;

[0163] Method 1: In an aprotic solvent, in the presence of a phenol catalyst, a base and light, a compound represented by Formula IA and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula VA;

[0164]

[0165] Method 2: In an aprotic solvent, in the presence of a phenol catalyst, a base and light, in the presence of a deuterated reagent or a tritiated reagent, a compound as shown in Formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula III-B;

[0166]

[0167] Method 3: In an aprotic solvent, in the presence of a phenol catalyst, a base and light, in the presence of a deuterated reagent or a tritiated reagent, a compound represented by formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by formula VC;

[0168]

[0169] In method 1, method 2 and method 3, the aprotic solvent, phenol catalyst, base, light, hydrogen source, compound as shown in formula IA, compound as shown in formula IB, compound as shown in formula IC, deuterated reagent and tritium reagent are as described above, and the temperature and reaction time of the reduction reaction are as described above.

[0170] The present invention also provides a use of a phenol catalyst as a reagent for converting an ester compound into an aldehyde or alcohol compound, wherein the phenol catalyst is as described above.

[0171] In the application, the phenol catalyst is further activated under alkaline reagent and light conditions.

[0172] Definition of terms:

[0173] Certain chemical groups defined herein are preceded by a shorthand notation to indicate the total number of carbon atoms present in the group. 1-4 Alkyl refers to an alkyl group as defined below having a total of 1, 2, 3 or 4 carbon atoms.

[0174] The term "substituted by" or "substituted with" means that any one or more hydrogen atoms on a particular atom are replaced by a substituent as long as the valence state of the particular atom is normal and the compound after the substitution is stable.

[0175] In the present invention, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0176] In the present invention, the term "alkyl" refers to a straight or branched saturated hydrocarbon group having a specified number of carbon atoms. Examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.

[0177] In the present invention, the term "alkenyl" refers to a straight or branched hydrocarbon group having one or more carbon-carbon double bonds and no carbon-carbon triple bonds. The one or more carbon-carbon double bonds may be internal (e.g., in 2-butenyl) or terminal (e.g., in 1-butenyl).

[0178] In the present invention, the term "alkynyl" refers to a straight or branched hydrocarbon group having one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds.

[0179] The term "alkylene" means a saturated divalent hydrocarbon group obtained by removing two hydrogen atoms from a saturated straight or branched hydrocarbon group; that is, one hydrogen in an alkyl group is replaced, and the definition of alkyl group is as described above. Examples of alkylene groups include methylene (-CH2-), ethylene {including -CH2CH2- or -CH(CH3)-}, isopropylene {including -CH(CH3)CH2-, -CH2CH(CH3)- or -C(CH3)2-}, and the like.

[0180] The term "cycloalkyl" refers to a carbocyclic group which is a saturated monocyclic or polycyclic ring system including fused, bridged or spiro rings.

[0181] The term "cycloalkenyl" refers to a partially unsaturated monocyclic or polycyclic (eg, bicyclic, tricyclic or more cyclic bridged, fused or spirocyclic) non-aromatic carbocyclic group having at least one double bond.

[0182] The term "heterocyclyl" includes "heterocycloalkyl" and "heterocycloalkenyl". "Heterocycloalkyl" refers to a stable saturated monocyclic or polycyclic (e.g., bicyclic, tricyclic or more cyclic bridged ring, fused ring or spiro ring system) cyclic group consisting of carbon atoms and 1, 2, 3, 4, 5 or 6 heteroatoms selected from N, O and S. "Heterocycloalkenyl" refers to a stable partially unsaturated monocyclic or polycyclic (e.g., bicyclic, tricyclic or more cyclic bridged ring, fused ring or spiro ring system) non-aromatic cyclic group consisting of carbon atoms and 1, 2, 3, 4, 5 or 6 heteroatoms selected from N, O and S with at least one double bond.

[0183] In the present invention, the term "alkoxy" refers to a cyclic or non-cyclic alkyl group connected via an oxygen bridge, and the definitions of alkyl and cycloalkyl are the same as described above.

[0184] In the present invention, "aryl" refers to a group having 6-14 atoms and zero heteroatoms, a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 shared p electrons in a cyclic array) ("C6-C 14 "aryl").

[0185] In the present invention, "heteroaryl" refers to a group ("5-10 membered heteroaryl") having carbon atoms and 1-4 heteroatoms provided in the aromatic ring system (wherein each heteroatom is independently selected from one or more of nitrogen, oxygen and sulfur, and the number of heteroatoms is 1, 2, 3 or 4). A monocyclic or bicyclic 4n+2 aromatic ring system (for example, having 6 or 10 shared p electrons in a cyclic array). In heteroaryl groups containing one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as long as the valence permits.

[0186] On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0187] The reagents and raw materials used in the present invention are commercially available.

[0188] The positive and progressive effects of the present invention are: the preparation method of aldehyde or alcohol compounds in the present invention has high yield, few by-products, wide substrate application range, and good functional group compatibility. The preparation method has cheap and easy-to-obtain reagents, simple operation, easy to scale up, and is suitable for industrial production and market promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0189] Figure 1 Schematic diagram of the photoreaction device. DETAILED DESCRIPTION

[0190] The present invention is further described in detail below in conjunction with the accompanying drawings and examples, but the protection scope of the present invention is not limited to the contents described above. The reagents and methods used in the examples are conventional reagents and methods unless otherwise specified.

[0191] The structural formula corresponding to the phenol catalyst in the following embodiments is as follows:

[0192]

[0193]

[0194]

[0195] The amount of phenol catalyst used in the following examples represents the molar percentage of the reaction substrate. For example, in Example 1, the amount of phenol catalyst used is 5.0 mol%, which means that the molar percentage of phenol catalyst to substrate 1 is 5.0%.

[0196] The following light reaction device of each embodiment is shown in FIG. Figure 1 shown.

[0197] Embodiment 1:

[0198]

[0199] Under nitrogen atmosphere, substrate 1 (0.30 mmol), phenol catalyst (5.0 mol% of 2,6-di-tert-butyl-4-phenylphenol, 2,4,6-triphenylphenol, 2,6-di-tert-butyl-4-(9-anthryl)phenol, 2,6-di-tert-butyl-4-heptylphenol, 3-phenyl-1-naphthol or 2-phenylphenol, respectively), hydrogen source (cesium formate, 0.36 mmol), base (cesium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol) were dissolved in solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 25°C and heated at 5W, 415 nm. The reaction was carried out for 16 hours with an LED lamp at a distance of 5 cm from the reaction device, and water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml×3), and the organic phases were combined, washed with water and saturated brine in sequence, dried over anhydrous sodium sulfate, concentrated and subjected to column chromatography to obtain 2 (when 2,6-di-tert-butyl-4-phenylphenol was used as a phenol catalyst, the yield was 85%, when 2,4,6-triphenylphenol was used as a phenol catalyst, the yield was 80%, when 2,6-di-tert-butyl-4-(9-anthryl)phenol was used as a phenol catalyst, the yield was 84%, when 2,6-di-tert-butyl-4-heptylphenol was used as a phenol catalyst, the yield was 80%, when 3-phenyl-1-naphthol was used as a phenol catalyst, the yield was 77%, and when 2-phenylphenol was used as a phenol catalyst, the yield was 75%; the purity of the above products was greater than 95%. 1 HNMR (600MHz, CDCl3): δ9.65(s,1H),3.97(br s,2H,),3.02-2.81(m,2H),2.47-2.36(m,1H),1.98-1.80(m,2H),1.59-1.50(m,2H),1.44(s,9H); 13 C NMR (150MHz, CDCl3): δ203.1,154.8,79.8,48.1,43.0,28.5,25.3.

[0200] Embodiment 2:

[0201]

[0202] Under a nitrogen atmosphere, substrate 3 (0.30 mmol), phenol catalyst (2,4,6-triphenylphenol, 10.0 mol%), hydrogen source (benzenethiol, 0.90 mmol), base (lithium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol) were dissolved in a solvent (toluene, 2.0 ml). After the addition, the reactants were placed at 15°C and irradiated with an 8-watt 455nm LED lamp at a distance of 5 cm from the reaction device for 10 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 4 (80% yield, purity greater than 95%). 1 H NMR (600MHz, CDCl3): δ9.73 (s, 1H), 2.44-2.37 (m, 3H), 2.01-1.67 (m, 12H); 13 C NMR (150MHz, CDCl3): δ206.1,56.7,38.0,37.2,33.7,28.3,28.0,27.6; HRMS(ESI)calcd for C 11 H 17 O + [M+H] + 165.1274, found 165.1273.

[0203] Embodiment 3:

[0204]

[0205] Under nitrogen atmosphere, substrate 5 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-(9-anthryl)phenol, 2.0 mol%), hydrogen source (cyclohexyl mercaptan, 0.60 mmol), base (potassium carbonate, 0.60 mmol), additive (tetrahydropyrrole, 0.60 mmol) were dissolved in solvent (1,4-dioxane, 5.0 ml). After the addition, the reactants were placed at 0°C and irradiated at a light source (5 watt 515 nm LED lamp, 20 watt white energy-saving lamp, 20 watt incandescent lamp) 5 cm away from the reaction device for 12 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 6 (when 515 nm When LED lamps were used as light sources, the yield was 85%, when white energy-saving lamps were used as light sources, the yield was 78%, and when incandescent lamps were used as light sources, the yield was 66%. The purity of the above products was greater than 95%). 1HNMR (300MHz, CDCl3): δ9.76 (t, J=1.8Hz, 1H), 5.41-5.28 (m, 2H), 2.42 (dt, J=7.2, 1.8Hz ,2H),2.08-1.91(m,4H),1.61(quint,J=7.2Hz),1.38-1.20(m,20H),0.87(t,J=6.6Hz); 13 C NMR (75MHz, CDCl3): δ202.8,130.1,129.7,44.0,32.0,29.9,29.7,29.6,29.5,29.4,29.3,29.2,29.1,29.0,27.3,22.8,22.2,14.29.HRMS(ESI)calcd for C 18 H 34 ON + [M+Na] + 289.2502, found 289.2504.

[0206] Embodiment 4:

[0207]

[0208] Under a nitrogen atmosphere, substrate 7 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-heptylphenol, 5.0 mol%), hydrogen source (2-methyl-2-imidazoline, 0.36 mmol), base (ammonium carbonate, 0.60 mmol), additive (morpholine, prolinol, tetrahydropyrrole or piperidine, 0.60 mmol) were dissolved in a solvent (methyl tert-butyl ether, 3.0 ml). After the addition, the reactants were placed at 40°C under a 5 W 405 nm LED lamp at a distance of 1.5 km from the reaction mixture. The reaction was irradiated at 8 cm from the device for 10 hours, and water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3), and the organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 8 (when morpholine was used as an additive, the yield was 86%, when prolinol was used as an additive, the yield was 88%, when tetrahydropyrrole was used as an additive, the yield was 84%, and when piperidine was used as an additive, the yield was 83%, and the purity of the above products was greater than 95%). 1 H NMR (300MHz, CDCl3): δ9.73 (s, 1H), 2.39 (dt, J = 7.2, 1.6Hz, 2H), 2.15 (dt, J = 6.9, 2.6Hz, 2H), 1.83 (t, J = 2.6Hz, 1H), 1.68-1.24 (m, 12H); 13C NMR (75MHz, CDCl3): δ202.6,84.3,68.1,43.9,29.2,29.1,28.9,28.6,28.4,22.1.

[0209] Embodiment 5:

[0210]

[0211] Under a nitrogen atmosphere, substrate 9 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-(1H-indol-3-yl)phenol, 5.0 mol%), hydrogen source (potassium formate, 0.90 mmol), base (cesium carbonate, 0.60 mmol), additive (dimethylamine, 0.60 mmol) were dissolved in a solvent (acetonitrile, 3.0 ml). After the addition, the reactants were placed at 15°C and irradiated with an 8-watt 455nm LED lamp at a distance of 3 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 10 (84% yield, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ9.84 (s, 1H), 7.80 (d, J = 12.0Hz, 2H), 6.97 (d, J = 12.0Hz, 2H), 3.84 (s, 3H); 13 C NMR (100MHz, CDCl3): δ190.9,164.6,131.9,129.9,114.3,55.5.

[0212] Embodiment 6:

[0213]

[0214] Under a nitrogen atmosphere, substrate 11 (0.30 mmol), phenol catalyst (α-naphthol, 5.0 mol%), hydrogen source (sodium formate, 0.90 mmol), base (ammonium hydroxide, 0.60 mmol), additive (prolinol, 0.60 mmol) were dissolved in a solvent (toluene, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 2-watt 395nm LED lamp at a distance of 6 cm from the reaction device for 12 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 12 (80% yield, purity greater than 95%). 1HNMR (400MHz, CDCl3): δ10.08(s,1H),8.33(d,J=9.0Hz,1H),7.86(d,J=3.1Hz,1H),7.45(d,J=9.2Hz,1H),7.35-7.32(m,2H); 13 CNMR (100MHz, CDCl3): δ185.2,135.3,125.2,124.4,123.0,121.9,119.7,111.5.

[0215] Embodiment 7:

[0216]

[0217] Under a nitrogen atmosphere, substrate 13 (0.30 mmol), phenol catalyst (9-phenanthroline, 5.0 mol%), hydrogen source (sodium formate, 0.90 mmol), base (sodium hydroxide, 0.60 mmol), additive (prolinol, 0.60 mmol) were dissolved in a solvent (cyclohexane, 3.0 ml). After the addition, the reactants were placed at 0°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 14 (81% yield, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ9.68 (d, J = 0.5Hz, 1H), 2.39–2.32 (m, 1H), 2.12–2.00 (m, 4H), 1.92–1.76 (m, 4H): 13 C NMR (100MHz, CDCl3): δ202.7,122.6(t, 1 J C-F =242.3Hz,CF2),47.2,32.2(t, 2 J C-F =24.6Hz,2×CH2),22.1(dd, 3 J C-F =5.8,4.5Hz,2×CH2); 19 F NMR (377MHz, CDCl3): δ-94.9 (d, J = 236Hz), -98.8 (d, J = 236Hz).

[0218] Embodiment 8:

[0219]

[0220] Under nitrogen atmosphere, substrate 15 (CAS: 1235-74-1, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (cesium formate, thiophenol, cyclohexyl mercaptan or 2-methyl-2-imidazoline, 0.40 mmol), base (potassium hydroxide, 0.60 mmol), additive (prolinol, 0.60 mmol) were dissolved in solvent (petroleum ether, 3.0 ml). After the addition, the reactants were placed at 35° C. and heated at 2 W at 395 nm. The reaction was irradiated with an LED lamp at a distance of 5 cm from the reaction device for 8 hours, and water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3), and the organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 16 (the yield was 85% when cesium formate was used as the hydrogen source, the yield was 82% when thiophenol was used as the hydrogen source, the yield was 86% when cyclohexyl mercaptan was used as the hydrogen source, and the yield was 80% when 2-methyl-2-imidazoline was used as the hydrogen source. The purity of the above products was greater than 95%). 1 H NMR (300MHz, CDCl3): δ9.29(s,1H),7.21(d,J=8.2Hz,1H),7.04(dd,J=8.1,2.0Hz,1H),6.92(d,J=1.5Hz,1H),3.00–2.77(m,3H),2.3 7(dt,J=13.0,2.6Hz,1H),1.98–1.75(m,4H),1.57–1.42(m,2H),1.41–1.31(m,2H),1.26(s,3H),1.25(d,J=6.9Hz,6H),1.19(s,3H); 13 CNMR (75MHz, CDCl3): δ206.1,146.2,145.9,134.4,127.0,124.1,124.0,49.8,42.8 ,37.8,36.2,33.4,32.0,29.7,25.1,24.0,23.9,21.3,17.7,14.0; HRMS(FD):calcd for C 20 H 28 O284.2140, found 284.2143.

[0221] Embodiment 9:

[0222]

[0223] Under a nitrogen atmosphere, substrate 17 (CAS: 4168-17-6, 0.30 mmol), phenol catalyst (3-phenyl-1-naphthol, 2.0 mol%), hydrogen source (1,3-cyclohexadiene, 0.36 mmol), base (sodium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 415 nm LED lamp at a distance of 5 cm from the reaction device for 10 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 18 (75% yield, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ9.51 (s, 1H), 7.83 (br s,1H),7.52(d,J=7.8Hz,1H),7.25(d,J=8.0Hz,1H),7.16(t,J=6.9Hz,1H),7.12(t,J=7. 9Hz,1H),5.99(d,J=7.8Hz,1H),3.95(s,1H),3.57-3.52(m,1H),3.45-3.35(m,2H),3.00 (d,J=8.6Hz,1H),2.94-2.88(m,2H),2.80-2.79(m,1H),2.56(dt,J=13.0,3.0Hz,1H),2. 37-2.32(m,1H),2.11-2.05(m,1H),1.77(dd,J=13.0,2.1Hz,1H),1.08(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3): δ201.4,148.2,135.2,134.0,129.0,124.3,123.0,119.5,118.1, 112.7,110.6,62.1,59.4,53.2,49.4,35.3,30.5,26.8,21.1,10.6; HRMS(ESI)calcdfor C 20 H 23 N2O + [M+H] + 307.1805, found 307.1799.

[0224] Embodiment 10:

[0225]

[0226] Under a nitrogen atmosphere, substrate 19 (0.30 mmol), phenol catalyst (3-hydroxy-2-phenylpyridine, 5.0 mol%), hydrogen source (p-methylthiophenol, 0.36 mmol), base (cesium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol), deuterated reagent (deuterated water, 3.00 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 15°C and irradiated with a 5-watt 405 nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 20 (86% yield, 95% deuterated rate, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ7.81 (d, J = 8.0Hz, 2H), 7.36 (d, J = 7.9Hz, 2H), 2.47 (s, 3H); 13 C NMR (100MHz, CDCl3): δ191.7,145.6,129.9,129.7,129.6,21.9.HRMS(ESI)calcd for C8H7DO + [M+H] + 122.0711, found 122.0711.

[0227] Embodiment 11:

[0228]

[0229] Under nitrogen atmosphere, substrate 21 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (cesium formate, 0.90 mmol), base (potassium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol), deuterated reagent (EtO 2 H, 6.00 mmol) was dissolved in a solvent (1,4-dioxane, 3.0 ml). After the addition, the reactants were placed at 50°C and irradiated with a 5-watt 415 nm LED lamp 5 cm away from the reaction device for 15 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and subjected to column chromatography to obtain 22 (82% yield, 97% deuteration rate, purity greater than 95%). 1H NMR (400MHz, CDCl3): δ8.36(s,1H),8.03(d,J=8.0Hz,1H),8.01–7.95(m,2H),7.93(d,J=8.9Hz,1H),7.73–7.64(m,1H),7.64–7.59(m,1H); 13 C NMR (100MHz, CDCl3): δ191.9(t,J=26.7Hz),136.5,134.5,134.1,132.7,129.5,129.1,129.1,128.1,127.1,122.8.HRMS(ESI)calcd for C 11 HkDJ + [M+H] + 158.0711, found 158.0709.

[0230] Embodiment 12:

[0231]

[0232] Under a nitrogen atmosphere, substrate 23 (0.30 mmol), phenol catalyst (4-acetyl-1-naphthol, 20.0 mol%), hydrogen source (formic acid, 0.36 mmol), base (sodium hydroxide, 0.90 mmol), additive (prolinol, 0.60 mmol), deuterated reagent (MeO 2 H, 3.00 mmol) was dissolved in a solvent (methyl tert-butyl ether, 3.0 ml). After the addition, the reactants were placed at 45° C. and irradiated with an 8-watt 455 nm LED lamp 5 cm away from the reaction device for 16 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and subjected to column chromatography to obtain 24 (86% yield, 98% deuteration rate, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ7.13(d,J=8.0Hz,2H),7.01(d,J=8.0Hz,2H),2.87(sept,J=6.9Hz,1H),2.75(s,2H),1.23(d,J=6.9Hz,6H),1.05(s,6H). 13 C NMR (100MHz, CDCl3): δ205.9 (t, J = 26.5Hz), 147.1, 134.1, 130.2, 126.2, 47.0, 42.9, 33.7, 24.0, 21.4.HRMS (ESI)calcd forC 14 H 19 DO +[M+H] + 206.1650, found 206.1643.

[0233] Embodiment 13:

[0234]

[0235] Under nitrogen atmosphere, substrate 25 (0.30 mmol), phenol catalyst (2-phenylphenol, 10.0 mol%), hydrogen source (ethanethiol, 0.36 mmol), base (cesium carbonate, 0.80 mmol), additive (piperidine, 0.60 mmol), deuterated reagent (MeCOO 2 H, 9.00 mmol) was dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 35° C. and irradiated with an 8-watt 455 nm LED lamp at a distance of 5 cm from the reaction device for 18 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and subjected to column chromatography to obtain 26 (84% yield, 95% deuteration rate, purity greater than 95%). 1 H NMR (400MHz, d6-DMSO): δ7.39–7.03(m,5H),2.82(t,J=7.6Hz,2H),2.53(t,J=7.6Hz,2H); 13 C NMR (100MHz, CDCl3): δ201.1 (t, J = 26.2Hz), 140.3, 128.6, 128.3, 126.3, 45.3, 28.1.HRMS (ESI)calcd forC9H 10 DO + [M+H] + 136.0867, found 136.0869.

[0236] Embodiment 14:

[0237]

[0238] Under nitrogen atmosphere, substrate 27 (0.30 mmol), phenol catalyst (3-((2,6-dimethylphenyl)amino)phenol, 5.0 mol%), hydrogen source (cyclohexylmercaptan, 0.36 mmol), base (sodium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol), deuterated reagent (iPrO 2H, 6.00 mmol) was dissolved in a solvent (ether, 3.0 ml). After the addition, the reactants were placed at 25° C. and irradiated with a 5 W 405 nm LED lamp 5 cm away from the reaction device for 26 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and subjected to column chromatography to obtain 28 (82% yield, 93% deuteration rate, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ7.29–7.20(m,2H),7.17–7.11(m,2H),3.37–3.24(m,3H),3.22–3.12(m,2H); 13 C NMR(100MHz, CDCl3): δ202.6(t,J=23.2Hz),141.1,126.8,124.6,50.7,32.9.HRMS(ESI)calcd for C 10 H 10 DO + [M+H] + 148.0867, found 148.0869.

[0239] Embodiment 15:

[0240]

[0241] Under nitrogen atmosphere, substrate 29 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (potassium formate, 0.90 mmol), base (cesium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol), tritiated reagent (tritium water, 6.00 mmol) were dissolved in solvent (ether, 3.0 ml). After addition, the reactants were placed at 15°C and irradiated with a 10-watt 475 nm LED lamp 5 cm away from the reaction device for 6 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 30 (82% yield, 95% tritiated rate, purity greater than 95%). Specific activity = 19 Ci mmol -1 , radiochemical purity = 96.0%. 1 H NMR (600MHz, CDCl3): 4.00-3.92 (m, 2H), 3.48 (ddd, J=11.5, 10.7, 2.6Hz, 2H, ),2.55-2.36(m,1H),1.89-1.83(m,2H),1.70(dtd,J=13.7,10.7,4.2Hz,2H);13 C{ 1 H}NMR (150MHz, CDCl3): δ203.0,66.8,46.9,25.8; 3 H NMR (426MHz, CDCl3): δ9.68 (d, J = 1.0Hz, 1 3 H); HRMS (ESI) calculation for C6H 10 3 HO2 + [M+H] + 117.0836, found 117.08376.

[0242] Embodiment 16:

[0243]

[0244] Under nitrogen atmosphere, substrate 31 (0.30 mmol), phenol catalyst (4'-aminophenyl-3-phenol, 10.0 mol%), hydrogen source (n-butyl mercaptan, 0.36 mmol), base (potassium carbonate, 0.60 mmol), additive (tetrahydropyrrole, 0.60 mmol), deuterated reagent (tritiated water, 6.00 mmol) were dissolved in solvent (ether, 3.0 ml). After addition, the reactants were placed at 25°C and irradiated with a 5W 415nm LED lamp at a distance of 5 cm from the reaction device for 8 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml x 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 32 (85% yield, 90% tritiated rate, purity greater than 95%). Specific activity = 15 Cimmol -1 , radiochemical purity = 98.0%. 1 H NMR (400MHz, CDCl3): δ, 4.10 (d, J = 13.4Hz, 2H), 2.60 (t, J = 12.8Hz, 2H), 2.4 0(td,J=7.6,2.0Hz,2H),1.70–1.50(m,5H),1.40(s,9H),1.20–1.00(m,2H); 13 C NMR (100MHz, CDCl3): δ202.4,154.9,79.4,43.9,41.2,35.6,32.0,28.6,28.5; 3 HNMR (426MHz, CDCl3): δ9.80 (t, J = 1.5Hz, 1 3 H); HRMS (ESI) calculation for C 13 H 23 3 HNO3+ [M+H] + 244.1833, found 244.1835.

[0245] Embodiment 17:

[0246]

[0247] Under nitrogen atmosphere, substrate 33 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (potassium formate, 0.36 mmol), base (cesium carbonate, 0.60 mmol), additive (prolinol, 0.60 mmol), tritiated reagent (tritium water, 6.00 mmol) were dissolved in solvent (ether, 3.0 ml). After addition, the reactants were placed at 25°C and irradiated with a 5W 415nm LED lamp at a distance of 5 cm from the reaction device for 10 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml x 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 34 (80% yield, 93% tritiated rate, purity greater than 95%). Specific activity = 17 Ci mmol -1 , radiochemical purity = 99.0%. 1 H NMR (400MHz, CDCl3): 8.17 (s, 1H), 7.82 (d, J = 8.40Hz, 1H), 7.43 (d, J = 8.40Hz, 1H), 7.18 (d, J = 2.80Hz, 1H), 6.67 (d, J = 2.40Hz, 1H), 3.87 (s, 3H); 13 C NMR (100MHz, CDCl3): δ192.5,140.0,130.7,129.3,128.2,126.4,121.8,109.7,103.2,33.1; 3 HNMR(426MHz, CDCl3): δ10.06(s,1 3 H); HRMS (ESI) calculation for C 10 H9 3 HNO + [M+H] + 162.0839, found 162.0838.

[0248] Embodiment 18:

[0249]

[0250] Under nitrogen atmosphere, substrate 1 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 2,4,6-triphenylphenol, 2,6-di-tert-butyl-4-(9-anthryl)phenol, 2,6-di-tert-butyl-4-heptylphenol, 3-phenyl-1-naphthol or 2-phenylphenol, 5.0 mol%), hydrogen source (cesium formate, 0.36 mmol), base (cesium carbonate, 0.60 mmol) were dissolved in solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 25° C. and irradiated with a 5 W 415 nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate ( 15 ml × 3), the organic phases were combined, washed with water and saturated brine in sequence, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 35 (when 2,6-di-tert-butyl-4-phenylphenol was used as the phenol catalyst, the yield was 99%, when 2,4,6-triphenylphenol was used as the phenol catalyst, the yield was 95%, when 2,6-di-tert-butyl-4-(9-anthryl)phenol was used as the phenol catalyst, the yield was 90%, when 2,6-di-tert-butyl-4-heptylphenol was used as the phenol catalyst, the yield was 95%, when 3-phenyl-1-naphthol was used as the phenol catalyst, the yield was 94%, when 2-phenylphenol was used as the phenol catalyst, the yield was 98%, and the purity of the above products was greater than 95%). 1 HNMR (600MHz, CDCl3): δ4.12(br s,2H),3.56-3.44(m,2H),2.69(brs,2H),1.75-1.68(m,2H),1.66-1.59(m,1H),1.45(s,9H),1.20-1.05(m,2H); 13 C NMR (150MHz, CDCl3): δ155.0,79.5,67.8,43.8,39.0,28.7,28.6.

[0251] Embodiment 19:

[0252]

[0253] Under a nitrogen atmosphere, substrate 5 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-(9-anthryl)phenol, 2.0 mol%), hydrogen source (cesium formate, 1,4-cyclohexadiene, p-methylthiophenol, cysteine, ethanethiol or cyclohexylthiol, 0.45 mmol), and base (potassium carbonate, 0.60 mmol) were dissolved in a solvent (1,4-dioxane, 5.0 ml). After the addition, the reactants were placed at 0°C and heated at 10 W, 515 nm. The reaction was carried out under an LED lamp 5 cm away from the reaction device for 12 hours, and water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3), and the organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 36 (when cesium formate was used as the hydrogen source, the yield was 97%, when 1,4-cyclohexadiene was used as the hydrogen source, the yield was 98%, when p-methylthiophenol was used as the hydrogen source, the yield was 95%, when cysteine ​​was used as the hydrogen source, the yield was 97%, when ethanethiol was used as the hydrogen source, the yield was 98%, when cyclohexyl mercaptan was used as the hydrogen source, the yield was 99%, and the purity of the above products was greater than 95%). 1 HNMR (300MHz, CD2Cl2): δ5.35(m,2H),3.58(t,J=6.6Hz,2H),2.03(q,J=5.8Hz,4H),1 .75(s,1H,OH),1.67–1.46(m,2H),1.38–1.23(m,22H),0.92–0.86(t,J=6.45Hz,3H); 13 C NMR (75MHz, CD2Cl2): δ130.3,130.2,63.2,33.4,32.4,30.6,30.3,30.2,30.0,29.8,29.8,27.7,27.4,26.3,23.2,14.4.

[0254] Embodiment 20:

[0255]

[0256] Under a nitrogen atmosphere, substrate 11 (0.30 mmol), phenol catalyst (α-naphthol, 5.0 mol%, 5.0 mol%), hydrogen source (sodium formate, 0.90 mmol), and base (ammonium hydroxide, 0.60 mmol) were dissolved in a solvent (toluene, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 2-watt 395 nm LED lamp at a distance of 5 cm from the reaction device for 12 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 37 (97% yield, purity greater than 95%). 1H NMR (300MHz, CDCl3): δ8.28(br s,1H),7.74-7.71(m,1H),7.38-7.34(m,1H),7.24-7.12(m,3H),4.87(s,2H),1.90(s,1H).

[0257] Embodiment 21:

[0258]

[0259] Under a nitrogen atmosphere, substrate 38 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-(4-tert-butylphenyl)phenol, 5.0 mol%), hydrogen source (cesium formate, 0.45 mmol), and base (potassium carbonate, 0.60 mmol) were dissolved in a solvent (N,N-dimethylformamide, 2.0 ml). After the addition, the reactants were placed at 0°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 39 (97% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ3.65–3.58(2H,m),3.52–3.35(2H,m),3.34–3.22(1H,m),3.10–3.04 (1H,m),2.65(1H,s),2.42–2.32(1H,m),2.01–1.85(1H,m),1.73–1.56(1H,m),1.42(9H,s); 13 C NMR (125MHz, CDCl3): δ154.6,79.0,63.7,48.6,48.1,45.3,44.9,41.1,40.3,28.3.

[0260] Embodiment 22:

[0261]

[0262] Under a nitrogen atmosphere, substrate 40 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (potassium formate, 0.90 mmol), and base (sodium carbonate, 0.60 mmol) were dissolved in a solvent (N,N-dimethylacetamide, 6.0 ml). After the addition, the reactants were placed at -10°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 10 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 41 (96% yield, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ7.11–7.04(m,2H),6.87–6.80(m,2H),4.32–4.28(m,1H),4.03–3.98(m,1H), 3.75–3.63(m,2H),2.91–2.86(m,1H),2.63–2.57(m,1H),2.33–2.23(m,1H),1.57(t,J=4.9Hz,1H); 13 C NMR (100MHz, CDCl3): δ154.6,130.0,127.3,121.0,120.5,116.6,67.6,63.5,34.8,27.4.HRMS(ESI)calcd for C 10 H 12 NaO2[M+Na] + 187.0730, found 187.0728.

[0263] Embodiment 23:

[0264]

[0265] Under a nitrogen atmosphere, substrate 42 (0.30 mmol), phenol catalyst (9,10-anthraquinone, 10.0 mol%), hydrogen source (1,2-dihydronaphthalene, 0.36 mmol), and base (cesium hydroxide, 0.60 mmol) were dissolved in a solvent (tert-butyl alcohol, 3.0 ml). After the addition, the reactants were placed at -20°C and irradiated with a 5-watt 415 nm LED lamp at a distance of 5 cm from the reaction device for 40 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 43 (91% yield, purity greater than 95%). 1H NMR (600MHz, CDCl3): δ4.09-3.78(m,4H),3.46(d,J=6.5Hz,2H),1.86(br s,1H),1.78-1.73(m,4H),1.56–1.50(m,3H),1.28–1.20(m,2H); 13 C{ 1 H}NMR(150MHz, CDCl3): δ109.1,67.8,64.2,39.2,34.2,26.7; HRMS(ESI)calcd for C9H 16 O3Na + [M+Na] + 195.0992, found 195.0989.

[0266] Embodiment 24:

[0267]

[0268] Under a nitrogen atmosphere, substrate 44 (0.30 mmol), phenol catalyst (cyanobiphenol, 20 mol%), hydrogen source (indoline, 0.36 mmol), and base (potassium hydroxide, 0.90 mmol) were dissolved in a solvent (n-hexane, 4.0 ml). After the addition, the reactants were placed at 50°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 15 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 45 (92% yield, purity greater than 95%). 1 H NMR (600MHz, CDCl3): δ5.40-5.31(m,6H),3.64(t,J=6.6Hz,2H),2.81(t,J=6.0Hz,4 H),2.09–2.01(m,4H),1.58-1.50(m,2H),1.38-1.29(m,10H),0.98(t,J=7.5Hz,3H). 13 C NMR (150MHz, CDCl3): δ132.0,130.3,128.3,127.7,127.1,63.1,32.8,29.6,29.5,29.4,29.2,27.2,25.7,25.6,20.6,14.3.

[0269] Embodiment 25:

[0270]

[0271] Under a nitrogen atmosphere, substrate 46 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-acetylphenol, 10 mol%), hydrogen source (2-benzyl-2-imidazoline, 0.30 mmol), and base (sodium hydroxide, 0.60 mmol) were dissolved in a solvent (tetrahydrofuran, 1.0 ml). After the addition, the reactants were placed at 80°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 10 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 47 (89% yield, purity greater than 95%). 1 H NMR (300MHz, CDCl3): δ3.60(t,J=6.7Hz,2H),2.16(dt,J=6.9,2.6Hz,2H),1.84(t,J=2.6Hz,1H),1.60-1.48(m,4H),1.44-1.28(m,10H); 13 C NMR (100MHz, CDCl3): δ84.8,68.2,63.1,32.9,29.6,29.5,29.2,28.9,25.6,18.6.

[0272] Embodiment 26:

[0273]

[0274] Under a nitrogen atmosphere, substrate 48 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-methoxyphenol, 5.0 mol%), hydrogen source (3-dihydropyrrole, 0.60 mmol), and base (ammonium hydroxide, 0.60 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 49 (91% yield, purity greater than 95%). 1 H NMR (300MHz, CDCl3): δ3.56 (t, J=6.6Hz, 4H), 1.74 (br s, 2H), 1.43-1.55 (m, 4H), 1.20-1.32 (m, 10H); 13 C NMR (125MHz, CDCl3): δ63.0, 32.7, 29.5, 29.3, 25.7.

[0275] Embodiment 27:

[0276]

[0277] Under a nitrogen atmosphere, substrate 50 (0.30 mmol), phenol catalyst (2,4,6-tri-tert-butylphenol, 2.0 mol%), hydrogen source (9,10-dihydrophenanthrene, 0.40 mmol), and base (tetramethylguanidine, 0.90 mmol) were dissolved in a solvent (ether, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with an 8-watt 470nm LED lamp at a distance of 5 cm from the reaction device for 10 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 51 (92% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ3.79(t,J=5.9Hz,2H),2.51(t,J=7.1Hz,2H),1.91(tt,J=7.1,5.9Hz,2H),1.57–1.44(m,1H); 13 C NMR (125MHz, CDCl3): δ119.6, 60.6, 28.2, 13.9.

[0278] Embodiment 28:

[0279]

[0280] Under a nitrogen atmosphere, substrate 52 (0.30 mmol), phenol catalyst (2,4,6-triphenylphenol, 0.5 mol%), hydrogen source (thioglycolic acid, 0.36 mmol), and base (cesium carbonate, 0.90 mmol) were dissolved in a solvent (methanol, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 53 (95% yield, purity greater than 95%). 1 HNMR (400MHz, CDCl3): δ4.18–4.04(m,4H),3.71(t,J=5.7Hz,2H),2.23(br s,1H),1.93–1.80(m,4H),1.33(t,J=7.3Hz,6H); 13 C NMR (100MHz, CDCl3): δ62.7, 61.9, 25.8, 22.8, 16.6. 31 P NMR(159MHz,CDCl3):δ32.7.HRMS(ESI)calcd for C7H17 NaO4P + [M+Na] + 219.0757, found 219.0760.

[0281] Embodiment 29:

[0282]

[0283] Under a nitrogen atmosphere, substrate 54 (0.30 mmol), phenol catalyst (2-tert-butyl-3,5-xylenol, 10.0 mol%), hydrogen source (ammonium formate, 0.90 mmol), and base (tetrabutylammonium hydroxide, 0.60 mmol) were dissolved in a solvent (isopropanol, 3.0 ml). After the addition, the reactants were placed at 22°C and irradiated with a 5-watt 415 nm LED lamp at a distance of 5 cm from the reaction device for 26 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 55 (86% yield, purity greater than 95%). 1 H NMR (300MHz, CDCl3): δ8.44–8.20(m,3H),8.11–7.89(m,2H),7.66–7.35(m,4H),3.82(t,J=6.2Hz,2H),3.77–3.68(m,2H),2.23–1.98(m,2H),1.58(br s,1H); 13 C NMR (100MHz, CDCl3): δ134.3,131.6,129.7,129.2,125.8,125.6,124.9,124.3,62.7,34.0,24.1.

[0284] Embodiment 30:

[0285]

[0286] Under a nitrogen atmosphere, substrate 56 (0.30 mmol), phenol catalyst (6-tert-butyl-2,4-xylenol, 10.0 mol%), hydrogen source (sodium sulfide, 0.39 mmol), and base (potassium tert-butoxide, 0.60 mmol) were dissolved in a solvent (tert-butanol, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 12 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and then column chromatographed to obtain 57 (93% yield, purity greater than 95%). 1HNMR (400MHz, CDCl3) δ8.24(br s,1H),6.70–6.68(m,1H),6.15–6.13(m,1H),5.95–5.94(m,1H),3.73(t,J=5.9Hz,2H),2.75(t,J=7.3Hz,2H),2.72(br s,1H),1.93–1.87(m,2H); 13 CNMR (100MHz, CDCl3): δ131.8,116.4,108.3,105.2,62.3,32.2,24.2.

[0287] Embodiment 31:

[0288]

[0289] Under a nitrogen atmosphere, substrate 58 (0.30 mmol), phenol catalyst (9-phenanthroline, 5.0 mol%), hydrogen source (cesium formate, 0.50 mmol), and base (1,8-diazabicyclo[5.4.0]undec-7-ene, 0.90 mmol) were dissolved in a solvent (toluene, 3.0 ml). After the addition, the reactants were placed at 0°C and irradiated with a 2-watt 390 nm LED lamp at a distance of 5 cm from the reaction device for 13 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 59 (92% yield, purity greater than 95%). 1 H NMR (400MHz, CDCl3): δ8.07 (br s,1H),7.61(dd,J=8.4,1.2Hz,1H),7.34(dd,J=7.2,1.2Hz,1H),7.20(ddd,J=7.2,7.2,1.2Hz,1H),7.12(dd d,J=8.4,7.2,1.2Hz,1H),7.02(d,J=2.4Hz,1H),3.89(t,J=6.4Hz,2H),3.02(dt,J=6.4,2.4Hz,2H),1.63(br s,1H).

[0290] Embodiment 32:

[0291]

[0292] Under a nitrogen atmosphere, substrate 60 (0.30 mmol), phenol catalyst (1-anthraquinone, 5.0 mol%), hydrogen source (tert-butyl mercaptan, 0.36 mmol), and base (tetramethylguanidine, 0.60 mmol) were dissolved in a solvent (n-hexane, 2.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 11 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and then column chromatographed to obtain 61 (89% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ3.99(t,J=8.5Hz,2H),3.78(d,J=6.6Hz,2H),3.68(dd,J=8.8,5.2Hz,2H),2.74–2.67(m,1H),1.43(s,9H); 13 C NMR (125MHz, CDCl3): δ156.6,79.6,64.8,30.6,28.5.

[0293] Embodiment 33:

[0294]

[0295] Under a nitrogen atmosphere, substrate 62 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-nitrophenol, 5.0 mol%), hydrogen source (potassium formate, 0.40 mmol), and base (cesium carbonate, 0.60 mmol) were dissolved in a solvent (cyclohexane, 3.0 ml). After the addition, the reactants were placed at -10°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 63 (90% yield, purity greater than 95%). 1 HNMR (500MHz, CD3OD): δ3.74 (s, 6H), 3.65 (s, 4H); 13 C NMR (125MHz, CD3OD): δ64.1, 60.8, 44.9.

[0296] Embodiment 34:

[0297]

[0298] Under a nitrogen atmosphere, substrate 64 (0.30 mmol), phenol catalyst (3,5-di-tert-butylcatechol, 2.0 mol%), hydrogen source (ammonium formate, 0.36 mmol), and base (lithium hydroxide, 0.60 mmol) were dissolved in a solvent (benzene, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 18 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and then column chromatographed to obtain 65 (96% yield, purity greater than 95%). 1 H NMR (400MHz, CD3OD): δ3.58–3.47(m,3H),3.26(dd,J=10.1,5.2Hz,1H),2.61–2.44(m,2H),2.19(dd,J=16.5,5.4Hz,1H). 13 C NMR (100 MHz, CD3OD): δ176.7,64.9,53.4,34.77,34.37,29.8.HRMS(ESI)calcd for C6H 10 NO2 + [M+H] + 130.0863, found 130.0864.

[0299] Embodiment 35:

[0300]

[0301] Under a nitrogen atmosphere, substrate 66 (0.30 mmol), phenol catalyst (4-phenylphenol, 5.0 mol%), hydrogen source (potassium formate, 0.90 mmol), and base (cesium carbonate, 0.60 mmol) were dissolved in a solvent (petroleum ether, 3.0 ml). After the addition, the reactants were placed at -20°C and irradiated with a 5-watt 405 nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 67 (92% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ4.23–1.18(m,1H),4.08(t,J=7.8Hz,1H),3.79–3.72(m,1H),3.69–3.65(m,1H),3.58–3.53(m,1H),2.42(br s,1H),1.41(s,3H),1.35(s,3H); 13C NMR (125MHz, CDCl3): δ109.4,76.2,65.7,62.9,26.7,25.2; HRMS (ESI)calcd for C6H 12 NaO3 + [M+Na] + 155.0679, found 155.0678.

[0302] Embodiment 36:

[0303]

[0304] Under a nitrogen atmosphere, substrate 68 (0.30 mmol), phenol catalyst (5,5'-di-tert-butyl-2,2'-biphenol, 1.0 mol%), hydrogen source (potassium formate, 0.70 mmol, 0.36 mmol), and base (sodium phosphate, 0.60 mmol) were dissolved in a solvent (acetonitrile, 6.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 455nm LED lamp at a distance of 5 cm from the reaction device for 28 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 69 (93% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): 8.41–8.40(m,1H),7.57–7.54(m,1H),7.13–7.07(m,2H),4.51(s,1H),3.95(t,J=5.6Hz,2H),2.96(t,J=5.6Hz,2H); 13 C NMR (125MHz, CDCl3): δ160.4,148.7,136.7,123.5,121.5,61.7,39.4.

[0305] Embodiment 37:

[0306]

[0307] Under a nitrogen atmosphere, substrate 70 (CAS: 608-16-2, 0.30 mmol), phenol catalyst (2-amino-4-tert-butylphenol, 10 mol%), hydrogen source (sodium formate, 0.90 mmol, 0.45 mmol), base (2,6-di-tert-butylpyridine, 0.60 mmol) were dissolved in a solvent (tetrahydrofuran: water = 9:1, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 15 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and then column chromatographed to obtain 71 (90% yield, purity greater than 95%). 1H NMR (400MHz, CD3OD): δ4.49(m,1H),4.31(dd,J=8,4.5Hz,1H),3.56(t,J=6.6Hz,2H),3.22(m, 1H),2.93(dd,J=12.8,4.9Hz,1H),2.71(d,J=12.8,1H),1.68–1.81(m,1H),1.35–1.66(m,7H); 13 C NMR (150MHz, CD3OD): δ164.7,62.0,61.5,60.2,55.7,39.6,32.0,28.7,28.4,25.5.

[0308] Embodiment 38:

[0309]

[0310] Under a nitrogen atmosphere, substrate 72 (CAS: 65-19-0, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 10 mol%), hydrogen source (1,4-cyclohexadiene, 0.36 mmol), and base (diisopropylethylamine, 0.60 mmol) were dissolved in a solvent (ethanol, 3.0 ml). After the addition, the reactants were placed at 0°C and irradiated with a 5-watt 450nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 73 (85% yield, purity greater than 95%). 1H NMR (400MHz, CDCl3): δ8.00(s,1H),7.51–7.48(m,1H),7.35–7.32(m,1H),7.19–7.0 9(m,2H),5.99(s,1H),3.43–3.38(m,1H),3.25–3.20(m,1H),3.19–3.14(m,1H),3.0 7–2.98(m,1H),2.87–2.75(m,3H),2.72–2.64(m,1H),2.60–2.53(m,1H),2.53–2.47 (m,1H),2.44–2.36(m,1H),2.31–2.24(m,1H),2.15–2.07(m,1H),1.76–1.63(m,2H).

[0311] Embodiment 39:

[0312]

[0313] Under a nitrogen atmosphere, substrate 74 (CAS: 631-71-0, 0.30 mmol), phenol catalyst (2,6-diphenylphenol, 5.0 mol%), hydrogen source (cyclohexyl mercaptan 0.90 mmol), and base (tetrapropylammonium hydroxide, 0.90 mmol) were dissolved in a solvent (ether, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 10-watt 600 nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 75 (88% yield, purity greater than 95%). 1 HNMR(400 MHz, CDCl3): δ5.81(s,1H),5.49–5.42(m,1H),4.25(s,1H),3.54–3.45(m,2H),2.37–1.92(m,6H),1.91–1.77(m,4H),1.67–1.52(m,5 H),1.53–1.40(m,4H),1.34–1.26(m,6H),1.26–1.20(s,3H),1.20–1.15(m,6H),1.09–0.98(m,8H),0.98–0.86(m,11H),0.81(s,4H). 13 C NMR (100 MHz, CDCl3): δ146.0,145.9,134.7,124.9,124.1,121.9,75.7,72.4,48.3,44.5,37.8,36.9,36.7,31.6,30.2,25.0,21.7,19.5,14.2.

[0314] Embodiment 40:

[0315]

[0316] Under a nitrogen atmosphere, substrate 76 (CAS: 1724-17-0, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 10 mol%), hydrogen source (potassium formate, 0.90 mmol), and base (potassium phosphate, 0.60 mmol) were dissolved in a solvent (1,4-dioxane, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 10-watt 515 nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 77 (85% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ5.18(t,J=3.55Hz,1H),3.54(d,J=10.90Hz,1H),3.20(d,J=10.90Hz,1H),3.21(d d,J=11.03,5.59Hz,1H),0.98(s,3H),0.93(s,3H),0.92(s,3H),0.87(s,3H),0.86(s,3H),0.77(s,3H); 13 C NMR (125MHz, CDCl3): δ144.2,122.4,122.3,79.0,69.7,55.2,47.6,46.5,42.3,41. 7,39.8,38.8,38.6,36.9,34.1,33.2,32.6,31.0,28.1,27.2,26.0,25.6,23.6,23.6 22.0,18.4,16.8,15.6.

[0317] Embodiment 41:

[0318]

[0319] Under a nitrogen atmosphere, substrate 78 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 10 mol%), hydrogen source (p-methylthiophenol, 0.40 mmol), and base (sodium phosphate, 0.60 mmol) were dissolved in a solvent (1,4-dioxane, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 10-watt 515 nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 79 (89% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ8.03(d,J=10.4Hz,1H),7.70–7.64(m,1H),7.44(d,J=11.5Hz,1H),7. 34(dd,J=7.5,1.7Hz,1H),7.30–7.22(m,2H),7.24–7.17(m,3H),7.15–7.08(m,2H),7.01(td ,J=7.4,1.6Hz,1H),4.63(t,J=5.9Hz,1H),4.46(dt,J=10.4,7.0Hz,1H),4.01(dp,J=11.5,7 .0Hz,1H),3.65–3.51(m,2H),3.14(dd,J=12.3,7.0Hz,1H),3.08–2.98(m,3H),1.92(s,2H); 13 C NMR (125MHz, CDCl3): δ172.6,172.2,137.2,136.4,128.8,128.5,127.9,127.0,123.3, 122.1,120.1,118.6,112.0,111.9,64.1,55.2,51.8,38.0,28.8,22.5; HRMS(ESI)calcd for C 22 H 25 N3NaO3 + [M+Na] + 402.1788, found 402.1789.

[0320] Embodiment 42:

[0321]

[0322] Under a nitrogen atmosphere, substrate 80 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-methylphenol, 15.0 mol%), hydrogen source (cysteine, 0.45 mmol), and base (rubidium hydroxide, 0.90 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 40°C and irradiated with a 5-watt 410 nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 81 (90% yield, purity greater than 95%). 1 H NMR (500MHz, CDCl3): δ3.87–3.93(m,1H),3.58–3.71(m,4H),3.23(td,J=4.4,9.5Hz,1H),1.59–1.49(m,26H),0.84–1.02(m,1H); 13 C NMR (125MHz, CDCl3): δ74.6,69.1,63.1,62.9,44.5,41.0,35.7,32.9,30.4,30.0,29.4,28.2,27.7,26.8,25.6,25.0,24.9,20.5.

[0323] Embodiment 43:

[0324]

[0325] Under a nitrogen atmosphere, substrate 82 (CAS: 564-20-5, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-hydroxymethylphenol, 10.0 mol%), hydrogen source (ethanethiol, 0.36 mmol), and base (potassium methoxide, 0.60 mmol) were dissolved in a solvent (cyclohexane, 2.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 415 nm LED lamp at a distance of 5 cm from the reaction device for 26 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 83 (92% yield, purity greater than 95%). 1H NMR (400MHz, CDCl3): δ3.78(dt,J=10.4,4.0Hz,1H),3.48–3.42(m,1H),1.90(dt,J=12.4,3.2Hz,1H),1.61-1.65(m,5H),1.35-1. 60(m,3H),1.29–1.24(m,2H),1.20(s,3H),1.16(dd,J=13.2,4.4Hz,1H),0.95(dd,J=12.0,2.0Hz,2H),0.88(s,3H),0.79(s,6H); 13 C NMR (100MHz, CDCl3): δ73.1,64.2,59.1,56.0,44.3,41.9,39.3,39.0,33.4,33.3,27.9,24.7,21.5,20.5,18.4,15.3.

[0326] Embodiment 44:

[0327]

[0328] Under a nitrogen atmosphere, substrate 84 (CAS: 122-32-7, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-(4-tert-butylphenyl)phenol, 15.0 mol%), hydrogen source (cesium formate, 1.80 mmol), and base (potassium carbonate, 0.60 mmol) were dissolved in a solvent (N,N-dimethylformamide, 4.0 ml). After the addition, the reactants were placed at 0°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 40 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and then column chromatographed to obtain 36 (89%, purity greater than 95%). 1 HNMR (300MHz, CD2Cl2): δ5.35(m,2H),3.58(t,J=6.6Hz,2H),2.03(q,J=5.8Hz,4H),1 .75(s,1H,OH),1.67–1.46(m,2H),1.38–1.23(m,22H),0.92–0.86(t,J=6.45Hz,3H); 13 C NMR (75MHz, CD2Cl2): δ130.3,130.2,63.2,33.4,32.4,30.6,30.3,30.2,30.0,29.8,29.8,27.7,27.4,26.3,23.2,14.4.

[0329] Embodiment 45:

[0330]

[0331] Under a nitrogen atmosphere, substrate 85 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-methylphenol, 5.0 mol%), hydrogen source (n-butyl mercaptan, 0.45 mmol), base (rubidium hydroxide, 0.90 mmol), deuterated reagent (deuterated water, 6.00 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 40°C and irradiated with a 5-watt 435nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 86 (95% yield, 95% deuterated rate, purity greater than 95%). 1 H NMR (300MHz, CDCl3): δ7.15–7.08(m,2H),6.86–6.82(m,2H),3.79(s,3H),2.65(t,J=7.7Hz,2H),1.85(t,J=7.7Hz,2H),1.37(br s,1H); 13 C{1H}NMR (75MHz, CDCl3): δ157.9,134.0,129.4,113.9,61.6(m),55.3,34.3,31.2.

[0332] Embodiment 46:

[0333]

[0334] Under a nitrogen atmosphere, substrate 87 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 20.0 mol%), hydrogen source (tert-butyl mercaptan, 0.30 mmol), base (potassium hydrogen phosphate, 0.90 mmol), deuterated reagent (deuterated water, 6.00 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 40°C and irradiated with a 5-watt 415 nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 88 (90% yield, 96% deuterated rate, purity greater than 95%). 1 H NMR (300MHz, CDCl3): δ7.23(m,2H),6.71(m,2H),2.93(s,6H),1.68(br,1H); 13C{1H}NMR(75MHz,CDCl3)δ150.4,129.0,128.7,112.7,64.6(m),40.7.

[0335] Embodiment 47:

[0336]

[0337] Under nitrogen atmosphere, substrate 89 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 9.0 mol%), hydrogen source (cyclohexyl mercaptan, 0.50 mmol), base (rubidium carbonate, 0.90 mmol), deuterated reagent (EtO 2 H, 6.00 mmol) was dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 40°C and irradiated with a 5W 405nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction. The aqueous phase was extracted with ethyl acetate three times (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 90 (93% yield, 98% deuteration rate, purity greater than 95%). 1H NMR (300MHz, CDCl3): δ5.36–5.32 (m, 2H), 2.05–1.95 (m, 4H), 1.58–1.50 (m, 2H), 1.46–1.18 (m, 22H), 0.88 (t, J = 6.7 Hz, 3H); 13 C{1H}NMR (75MHz, CDCl3): δ130.0,129.9,62.4(m),32.7,32.0,29.9,29.8,29.6,29.5,29.4,29.3,27.3,25.8,22.8,14.2.

[0338] Embodiment 48:

[0339]

[0340] Under a nitrogen atmosphere, substrate 91 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 9.0 mol%), hydrogen source (cyclohexyl mercaptan, 0.50 mmol), base (rubidium carbonate, 0.90 mmol), deuterated reagent (deuterated water, 6.00 mmol) were dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 40°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 92 (90% yield, 96% deuterated rate, purity greater than 95%). 1 H NMR (500MHz, CDCl3) δ7.29–7.17(m,5H),4.28(dd,J=8.5,7.1Hz,1H),4.18(dd ,J=8.5,7.2Hz,1H),3.62–3.54(m,1H),3.58–3.48(m,1H),2.76–2.62(m,2H); 13 C NMR (125MHz, CDCl3): δ137.9,129.4,129.2,127.3,65.6,56.1,39.4; HRMS(ESI)calcd for C9H 12 2 H2NO + [M+H] + 154.1195, found 154.1196.

[0341] Embodiment 49:

[0342]

[0343] Under a nitrogen atmosphere, substrate 93 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (ethanethiol, 0.45 mmol), base (potassium carbonate, 0.90 mmol), deuterated reagent (MeO 2 H, 6.00 mmol) was dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 40°C and irradiated with a 2-watt 390 nm LED lamp at a distance of 5 cm from the reaction device for 20 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and subjected to column chromatography to obtain 94 (95% yield, 95% deuteration rate, purity greater than 95%). 1H NMR (500MHz, CDCl3): δ7.16-7.07(m,2H), 6.92-6.82(m,2H), 2.79(t,J=6.8,2H), 1.88(t,J=6.8,2H); 13 C NMR (125MHz, CDCl3): δ154.7,130.7,127.7,127.2,120.9,116.3,60.4(m),32.1,25.2.

[0344] Embodiment 50:

[0345]

[0346] Under a nitrogen atmosphere, substrate 95 (CAS: 2868-48-6, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 10.0 mol%), hydrogen source (benzenethiol, 0.45 mmol), base (cesium carbonate, 0.90 mmol), deuterated reagent (MeO 2 H, 6.00 mmol) was dissolved in a solvent (tetrahydrofuran, 3.0 ml). After the addition, the reactants were placed at 25° C. and irradiated with a 2-watt 390 nm LED lamp 5 cm away from the reaction device for 20 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml×3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and subjected to column chromatography to obtain 96 (90% yield, 93% deuteration rate, purity greater than 95%). 1H NMR (500MHz, CDCl3): δ3.49-3.59(m,2H),1.94(dt,J=12.0,3.5Hz,1H),1.77-1.86(m,1H),1.68-1.76(m,3H),1.49-1 .63(m,7H),1.29-1.46(m,9H),1.13-1.27(m,4H),0.91-1.11(m,4H),0.88(s,3H),0.87(d,J=7.0Hz,3H),0.61(s,3H); 13 C NMR (125MHz, CDCl3): δ71.5,71.4,62.8(m),55.8,55.1,43.8,42.5,40.2,39.2,3 7.3,36.8,35.5,35.0,34.1,31.9,30.4,29.2,28.8,26.9,23.4,21.2,18.8,12.1.

[0347] Embodiment 51:

[0348]

[0349] Under nitrogen atmosphere, substrate 97 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 7.0 mol%), hydrogen source (cyclohexyl mercaptan, 0.36 mmol), base (sodium carbonate, 0.60 mmol), tritiated reagent (tritium water, 6.00 mmol) were dissolved in solvent (ether, 3.0 ml). After addition, the reactants were placed at 25°C and irradiated with a 5-watt 455 nm LED lamp 5 cm away from the reaction device for 16 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 98 (90% yield, 90% tritiated rate, purity greater than 95%). Specific activity = 31 Ci mmol -1 , radiochemical purity = 99.0%. 1 H NMR (500MHz, CDCl3): δ6.60 (br s,1H),3.46–3.42(m,1H),3.12–3.07(m,1H),2.45–2.40(m,1H),2.35– 2.30(m,1H),1.98–2.08(m,1H),1.86–1.96(m,1H),1.51–1.59(m,1H); 13 C NMR (125MHz, CDCl3): δ172.8,64.2,44.7,35.7,30.2,23.4; 3 H NMR(426MHz, CDCl3):3.65–3.61(m,1 3 H), 3.56–3.52(m.1 3 H).HRMS(ESI)calcd for C6H 10 3 H2NO2 + [M+H] + 134.1027, found 134.1028.

[0350] Embodiment 52:

[0351]

[0352] Under nitrogen atmosphere, substrate 99 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 5.0 mol%), hydrogen source (n-butyl mercaptan, 0.45 mmol), base (sodium phosphate, 0.60 mmol), tritiated reagent (tritium water, 6.00 mmol) were dissolved in solvent (ether, 3.0 ml). After addition, the reactants were placed at 25°C and irradiated with a 5-watt 415 nm LED lamp 5 cm away from the reaction device for 16 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated and column chromatographed to obtain 100 (92% yield, 91% tritiated rate, purity greater than 95%). Specific activity = 30 Ci mmol -1 , radiochemical purity = 98.0%. 1 H NMR (400MHz, CDCl3): δ8.29(br s,1H),7.16–7.11(m,1H),7.06(dd,J=7.4,1.6Hz,1H),6.90–6.83(m,2H),3.47(br s,1H),2.90–2.84(m,2H). 13 C NMR (100MHz, CDCl3) δ155.1,131.1,128.3,126.6,120.6,116.7,77.1,64.3,34.5: 3 H NMR(426MHz, CDCl3):3.94–3.88(m,2 3 H).HRMS(ESI)calcd for C8H9 3 H2O2 + [M+H] + 143.0918, found 143.0919.

[0353] Embodiment 53:

[0354]

[0355] Under nitrogen atmosphere, substrate 101 (0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 2.0 mol%), hydrogen source (cyclohexyl mercaptan, 0.60 mmol), base (cesium carbonate, 0.60 mmol), tritiated reagent (tritium water, 6.00 mmol) were dissolved in solvent (ether, 3.0 ml). After addition, the reactants were placed at 25°C and irradiated with a 5-watt 405 nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain 102 (92% yield, 90% tritiated rate, purity greater than 95%). Specific activity = 29 Ci mmol -1 , radiochemical purity = 99.0%. 1 H NMR (600MHz, CDCl3): δ6.81 (d, J = 1.7Hz, 1H), 6.79–6.70 (m, 2H), 5.91 (s, 2H), 2.47 (br s, 1H); 13 C NMR (150MHz, CDCl3): δ147.8,147.1,135.0,120.5,108.2,107.9,101.0,65.1; 3 H NMR(426MHz, CDCl3): δ4.50(s,2 3 H).HRMS(ESI)calcd for C8H7 3 H2O3 + [M+H] + 157.0711, found 157.0712.

[0356] Embodiment 54:

[0357]

[0358] Under nitrogen atmosphere, the substrate 103 (CAS: 50998-13-5, 0.30 mmol), phenol catalyst (2,6-di-tert-butyl-4-phenylphenol, 2.0 mol%), hydrogen source (cyclohexyl mercaptan, 0.60 mmol), base (cesium carbonate, 0.60 mmol), tritiated reagent (tritium water, 6.00 mmol) were dissolved in a solvent (ether, 3.0 ml). After the addition, the reactants were placed at 25°C and irradiated with a 5-watt 405nm LED lamp at a distance of 5 cm from the reaction device for 16 hours. Water was added to quench the reaction. The aqueous phase was extracted three times with ethyl acetate (15 ml × 3). The organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and then column chromatographed to obtain 104 (88% yield, 91% tritiated rate, purity greater than 95%). Specific activity = 28Ci mmol-1 , radiochemical purity = 98.0%. 1 H NMR (500 MHz, CDCl3): δ 7.53 (d, J = 11.7 Hz, 1H), 5.14 (s, 1H), 4.53 (dd, J = 8.0, 2.2 Hz, 2H), 4.32 (t, J = 8.1 Hz, 1H), 4.28–4.18 (m, 2H), 4.14 (dqd, J = 8.2, 7.0, 2.6 Hz, 1H), 4.06 (td, J = 7.0, 2.5 Hz, 1H), 3.90 (dtd, J = 11.7, 7.1, 2.5 Hz, 1H), 3.81–3.65 (m, 3H), 3.63 (dd, J = 12.5, 8.1 Hz, 1H), 3.60–3.45 (m, 2H), 2.04 (dd, J = 12.5, 7.0 Hz, 1H), 2.01 (s, 2H), 1.95 (dd, J = 12.3, 7.0 Hz, 1H); 13 C NMR (125 MHz, CDCl3): δ 175.9, 97.5, 73.1, 72.6, 71.0, 69.5, 68.0, 64.9, 53.7, 40.3, 22.7; 3 H NMR (426 MHz, CDCl3): δ 3.75–3.70 (m, 1 3 H), 3.60–3.65 (m, 1 3 H); HRMS (ESI) calcd for C 11 H 20 3 H2NO8 + [M + H] + 300.1510, found 300.1512.

Claims

1. A method for preparing an aldehyde compound, characterized in that: The method comprises the following steps: in a solvent, under the conditions of a phenol catalyst, a base, an additive and light, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment II; Wherein, the fragment I is The fragment II is The phenol catalyst is Ring A is C 6-14 Aryl or 5-10 membered heteroaryl; the heteroatom in the 5-10 membered heteroaryl is selected from one or more of N, O and S, and the number of heteroatoms is 1-4; R 1 Each independently is H, C 1-10 Alkyl, -OR 1a 、-NO2、-(C=O)R 1b 、-NR 1c R 1d , C 6-14 Aryl, 5-10 membered heteroaryl, substituted by one or more R 1e Substituted C 1-10 Alkyl, with one or more R 1f Substituted C 6-14 Aryl, or one or more R 1g substituted 5-10 membered heteroaryl; the 5-10 membered heteroaryl and one or more R 1g The heteroatom in the substituted 5-10 membered heteroaryl is selected from one or more of N, O and S, and the number of the heteroatoms is 1-4; m is 1, 2, 3, 4 or 5; R 1a and R 1b are independently H or C 1-10 alkyl; R 1c and R 1d Independently H, C 6-14 Aryl, or substituted by one or more R 1a-1 C 6-14 Aryl; R 1e , R 1f and R 1g Each independently is -OH, C 1-10 Alkyl, NR 1a-2 R 1a-3 、-(C=O)R 1a-4 or -CN; R 1a-1 , R 1a-2 , R 1a-3 and R 1a-4 are independently H or C 1-10 alkyl; The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment II; The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene group in the fragment I is directly connected; the carbonyl group in the fragment I is not connected to N, O and S.

2. The method for preparing an aldehyde compound according to claim 1, characterized in that: The preparation method of the aldehyde compound meets one or more of the following conditions: (1) The solvent is one or more of an alkane solvent, an aromatic solvent, an ether solvent, a nitrile solvent, an alcohol solvent, an amide solvent, a sulfoxide solvent, water and pyridine; the alkane solvent is preferably n-hexane, cyclohexane, heptane, n-pentane, petroleum ether or gasoline; the aromatic solvent is preferably benzene, toluene, xylene or trimethylbenzene; the ether solvent is preferably tetrahydrofuran, diethyl ether, isopropyl ether, 1,4-dioxane or methyl tert-butyl ether; the nitrile solvent is preferably acetonitrile; the alcohol solvent is preferably methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol or tert-butanol; the amide solvent is preferably N,N-dimethylformamide or N,N-dimethylacetamide; the sulfoxide solvent is preferably dimethyl sulfoxide; (2) the concentration of the compound containing fragment I in the solvent is 0.05-0.75 mol / L, for example, 0.06 mol / L, 0.075 mol / L, 0.10 mol / L, 0.15 mol / L or 0.30 mol / L; (3) the molar ratio of the phenol catalyst to the compound containing fragment I is (0.005-0.2):1, preferably (0.01-0.15):1, for example 0.02:1, 0.05:1, 0.07:1, 0.09:1 or 0.10:1; (4) The base is sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, ammonium carbonate, triethylmethyl methyl ammonium carbonate, tributylmethyl methyl ammonium carbonate, potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tributylbenzylammonium hydroxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, triethylamine, trimethylamine, diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylguanidine, tetramethylethylenediamine, N-methylmorpholine, N,N,N',N",N"-pentamethyldiethylenetriamine or a phosphazene base, preferably lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, ammonium carbonate, cesium hydroxide, ammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, tetramethylguanidine, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, potassium tert-butoxide, potassium methoxide, DBU, 2,6-di-tert-butylpyridine or diisopropylethylamine; (5) The molar ratio of the base to the compound containing fragment I is (0.2-5):1, more preferably (2-3):1, for example 2.7:1; (6) The additive is Among them, R A1 and R A2 Independently for C 1-4 Alkyl; R A3 H, C 1-4 Alkyl, -C 1-4 Alkylene -OH or -C 1-4 Alkylene-NH2; X 1 is -CH2-, -O- or -NH-; n is 0, 1 or 2; (7) The molar ratio of the additive to the compound containing fragment I is (1-5):1, for example 2:1; (8) The hydrogen source is R B1 -SH, HCO2H, H2S, alkali metal sulfides, dihydrogenated C 6-14 Aryl, dihydrogenated 5-10 membered heteroaryl, B3 Substituted dihydrogenated C 6-14 Aryl, or one or more R B4 substituted dihydrogenated 5-10 membered heteroaryl; said dihydrogenated 5-10 membered heteroaryl and substituted by one or more R B4 The heteroatom in the substituted dihydrogenated 5-10 membered heteroaryl is selected from one or more of N, O and S, and the number of the heteroatoms is 1-4; Among them, R B1 C 1-4 Alkyl, C 3-10 Cycloalkyl, -C 1-4 Alkylene-CO2H, (C 1-4 Alkyl)3Si-, C 6-14 Aryl, or one or more R B1-1 Substituted C 6-14 Aryl; R B2 C 1-4 Alkyl, C 3-10 Cycloalkyl, (C 1-4 Alkyl)3Si-, C 6-14 Aryl, or one or more R B2-1 Substituted C 6-14 Aryl; R B1-1 and R B2-1 Each independently is C 1-4 alkyl; R B3 and R B4 Each independently is C 1-4 Alkyl or -CH2Ph; independently an alkali metal ion or NH4 + ; (9) The molar ratio of the amount of the hydrogen source to the compound containing fragment I is (1.0-6.0):1, preferably (1.0-3.0):1, for example 1.1:1, 1.2:1, 1.3:1, 1.5:1, 1.7:1, 2.0:1 or 2.3:1; (10) The light source of the illumination is an LED lamp, an incandescent lamp or an energy-saving lamp; the power of the LED lamp is preferably 2-10 watts, such as 5-8 watts; the power of the incandescent lamp is preferably 20 watts; the power of the energy-saving lamp is preferably 20 watts; (11) The light source of the illumination is 3-8 cm away from the reaction device, for example, 5-6 cm; (12) The wavelength of the illumination is a single wavelength or a mixed wavelength; the wavelength of the single wavelength is preferably 390-600 nm, more preferably 395-515 nm, such as 400 nm, 405 nm, 410 nm, 415 nm, 435 nm, 450 nm, 455 nm, 470 nm or 475 nm; the range of the mixed wavelength is preferably 400 nm-550 nm; (13) The reaction temperature of the reduction reaction is -20°C to 80°C, preferably -10°C to 50°C, for example, 0°C, 15°C, 25°C, 22°C, 35°C, 40°C or 45°C; (14) In the method for preparing the aldehyde compound, the reagents for the reduction reaction are the solvent, the phenol catalyst, the base, the additive, the compound containing fragment I and the hydrogen source.

3. The method for preparing an aldehyde compound according to claim 2, characterized in that: The preparation method of the aldehyde compound meets one or more of the following conditions: (1) The solvent is a mixed solvent of an ether solvent and water, such as tetrahydrofuran and water; (2) The phenol catalyst is any of the following compounds: (3) The additive is prolinol, tetrahydropyrrole, morpholine, dimethylamine or piperidine; (4) R B1 -SH is thiophenol, p-methylthiophenol, cyclohexylmercaptan, ethylmercaptan, n-butylmercaptan, tert-butylmercaptan, thioglycolic acid, cysteine ​​or triisopropylsilanethiol; (5) is cesium formate, potassium formate, sodium formate or ammonium formate; (6) The alkali metal sulfide is sodium sulfide; (7) The dihydrogenated C 6-14 Aryl is 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,2-dihydronaphthalene or 9,10-dihydrophenanthrene; (8) The dihydrogenated 5-10 membered heteroaryl group is indoline or 3-dihydropyrrole; (9) The one or more R B4 The substituted dihydrogenated 5- to 10-membered heteroaryl is 2-methyl-2-imidazoline or 2-benzyl-2-imidazoline.

4. The method for preparing an aldehyde compound according to claim 1, wherein: The preparation method of the aldehyde compound is the following method 1, method 2 or method 3; Method 1: In a solvent, under the conditions of a phenol catalyst, a base, an additive and light, a compound represented by Formula IA and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula II-A; Method 2: In a solvent, under the conditions of a phenol catalyst, a base, an additive and light, a compound represented by formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by formula II-B; Method 3: In a solvent, under the conditions of a phenol catalyst, a base, an additive and light, a compound represented by Formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula II-C; In method 1, method 2 and method 3, the solvent, phenol catalyst, base, additive and light conditions are as described in any one of claims 1 to 3; Among them, R 2 For-LR 2a , C 1-10 Alkyl, C 3-20 Cycloalkyl, C 6-14 Aryl, 5-10 membered heteroaryl, C 3-25 Cycloalkenyl, 3-25 membered heterocyclic group, 2b Substituted C 1-10 Alkyl, with one or more R 2c Substituted C 3-20 Cycloalkyl, with one or more R 2d Substituted C 6-14 Aryl, one or more R 2e substituted 5-10 membered heteroaryl, substituted by one or more R 2f Substituted C 3-25 Cycloalkenyl, or one or more R 2g substituted 3-25 membered heterocyclyl; L is -C 1-10 Alkylene-C(R 2a-1 R 2a-2 )-; R 2a C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-14 Aryl, or one or more R 2a-3 Substituted C 6-14 Aryl; R 2a-1 and R 2a-2 Independently H, C 1-4 Alkyl or -NH2; R 2a-3 C 1-4 Alkyl or C 1-4 Alkoxy; R 2b -OH, -CN, -N(R 2b-3 R 2b-4 ), 5-10 membered heteroaryl, 3-25 membered heterocyclic group, C 3-20 Cycloalkyl, with one or more R 2b-5 Substituted C 3-20 Cycloalkyl, or one or more R 2b-6 substituted 3-25 membered heterocyclyl; R 2b-1 and R 2b-2 Independently for C 1-4 alkyl; R 2b-3 and R 2b-4 Independently H, C 1-4 Alkyl or And R 2b-3 and R 2b-4 Not at the same time H; R 2b-5 and R 2b-6 are independently -OH, C 1-4 Alkyl or oxo (=O); R 2c , R 2d , R 2e , R 2f and R 2g are independently halogen, -OH, oxo (=O), C 1-4 Alkyl, C 1-4 Alkoxy, -N(R 2d-1 R 2d -2 ), or C substituted by one or more hydroxyl groups 1-4 alkyl; R 2d-1 and R 2d-2 Independently H, C 1-4 Alkyl, -(C=O)C 1-4 Alkyl or -(C=O)OC 1-4 alkyl; The 5-10 membered heteroaryl, 3-25 membered heterocyclic group, 2e substituted 5-10 membered heteroaryl, substituted by one or more R 2g substituted 3-25 membered heterocyclic group and one or more R 2b-6 The heteroatom or heteroatom group in the substituted 3-25 membered heterocyclic group is selected from N, O, S and -(NR 7 )-, the number of heteroatoms is 1-4; R 7 H or -(C=O)OC 1-4 alkyl; R 3 , R 5 and R 6 Independently for C 1-10 Alkyl, C 3-20 Cycloalkyl, C 6-14 Aryl, one or more R 3a Substituted C 1-10 Alkyl or R 3a each independently is -OH; R 4 For -C 3-20 Cycloalkyl-; Ring B is C 3-20 Cycloalkyl, C 6-14 Aryl, one or more R C1 Substituted C 3-20 Cycloalkyl, or one or more R C2 Substituted C 6-14 Aryl; R C1 and R C2 Independently for C 1-4 alkyl; p is 1, 2 or 3.

5. The method for preparing an aldehyde compound according to claim 4, characterized in that: The preparation method of the aldehyde compound meets one or more of the following conditions: (1)R 2 , R 3 , R 5 and R 6 In the C 1-10 Alkyl, with one or more R 2b Substituted C 1-10 Alkyl and one or more R 3a Substituted C 1-10 C in the alkyl group 1-10 The alkyl groups are independently C 1-4 Alkyl or C 6-10 Alkyl; the C 1-4 The alkyl group is preferably methyl, ethyl, n-propyl, n-butyl or tert-butyl; 6-10 The alkyl group is preferably (2)R 2 , R 2b , R 3 , R 5 and R 6 In the C 3-20 Cycloalkyl, with one or more R 2c Substituted C 3-20 Cycloalkyl and one or more R 2b-5 Substituted C 3-20 C in cycloalkyl 3-20 The cycloalkyl groups are independently C 3-8 Cycloalkyl or C 10-20 Cycloalkyl; said C 3-8 The cycloalkyl group is preferably cyclobutyl or cyclohexyl; 10-20 The cycloalkyl group is preferably (3) In ring B, the C 3-20 Cycloalkyl and one or more R C1 Substituted C 3-20 C in cycloalkyl 3-20 The cycloalkyl groups are independently C 6-10 Cycloalkyl, preferably (4)R 2 , R 2a , R 3 , R 5 and R 6 In the C 6-14 Aryl, one or more R 2d Substituted C 6-14 Aryl and one or more R 2a-3 Substituted C 6-14 C in aromatic groups 6-14 Aryl is independently phenyl, naphthyl or anthracenyl; (5) In ring B, the C 6-14 Aryl and one or more R C2 Substituted C 6-14 C in aromatic groups 6-14 Aryl is independently phenyl; (6)R 2 and R 2b wherein the 5-10 membered heteroaryl group and one or more R 2e The 5-10 membered heteroaryl in the substituted 5-10 membered heteroaryl is independently pyrrolyl, pyridyl or indolyl; (7)R 2 In the C 3-25 Cycloalkenyl and one or more R 2f Substituted C 3-25 C in cycloalkenyl 3-25 The cycloalkenyl groups are independently C 10-25 Cycloalkenyl, preferably (8)R 2 and R b wherein the 3-25 membered heterocyclic group is replaced by one or more R 2g substituted 3-25 membered heterocyclic group and one or more R 2b-6 The 3-25-membered heterocyclic group in the substituted 3-25-membered heterocyclic group is independently a 5-10-membered heterocyclic group and a 15-25-membered heterocyclic group; the 5-10-membered heterocyclic group is preferably a tetrahydropyrrolyl, a piperidinyl, a pyranyl, The 15-25 membered heterocyclic group is preferably (9) In L, the -C 1-10 Alkylene-C(R 2a-1 R 2a-2 )-C 1-10 Alkylene is methylene, (10)R 2a In the C 2-20 Alkenyl is C 8-12 Alkenyl, e.g. (11)R 2a In the C 2-20 Alkynyl is C 2-6 Alkynyl groups, such as ethynyl; (12)R 2a-1 , R 2a-2 , R 2a-3 , R 2b-1 , R 2b-2 , R 2b-3 , R 2b-4 , R 2b-5 , R 2b -6. R 2c , R 2d , R 2e , R 2f , R 2g , R 2d-1 , R 2d-2 , R 7 , R C1 and R C2 In the C 1-4 Alkyl, -(C=O)C 1-4 Alkyl, -(C=O)OC 1-4 Alkyl and C substituted by one or more hydroxyl groups 1-4 C in the alkyl group 1-4 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; (13)R 2c , R 2d , R 2e , R 2f and R 2g wherein the halogen is independently fluorine, chlorine, bromine or iodine; (14)R 2a -3. R 2c , R 2d , R 2e , R 2f and R 2g In the C 1-4 Alkoxy is independently methoxy; (15)R 4 In the -C 3-20 Cycloalkyl- is -C 5-10 Cycloalkyl-, e.g.

6. The method for preparing an aldehyde compound according to claim 4, characterized in that: The preparation method of the aldehyde compound meets one or more of the following conditions: (1)R 2 for (2)R 3 Methyl, ethyl, tert-butyl, Phenyl, cyclohexyl or (3)R 4 for (4)R 5 and R 6 are independently methyl; (5) Ring B is 7. The method for preparing an aldehyde compound according to any one of claims 4 to 6, characterized in that: The preparation method of the aldehyde compound meets one or more of the following conditions: (1) The compound represented by IA is selected from any of the following compounds: (2) The compound shown in IB is (3) The compound represented by IC is selected from any of the following compounds:

8. A method for preparing a deuterated or tritiated aldehyde compound, characterized in that: The method comprises the following steps: in an aprotic solvent, under the conditions of a phenol catalyst, a base, an additive and light, in the presence of a deuterated reagent or a tritium reagent, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment III; Wherein, the fragment I is The fragment III is The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment III; The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene in the fragment I is directly connected; the carbonyl in the fragment I is not connected to N, O and S; The phenol catalyst, base, additive, light and hydrogen source are as described in any one of claims 1-3.

9. The method for preparing a deuterated or tritiated aldehyde compound according to claim 8, characterized in that: The preparation method of the deuterated or tritiated aldehyde compound meets one or more of the following conditions: (1) The aprotic solvent is one or more of an alkane solvent, an aromatic solvent, an ether solvent, a nitrile solvent and a sulfoxide solvent; the alkane solvent is preferably n-hexane, cyclohexane, heptane, n-pentane, petroleum ether or gasoline; the aromatic solvent is preferably benzene, toluene, xylene or trimethylbenzene; the ether solvent is preferably tetrahydrofuran, diethyl ether, isopropyl ether, 1,4-dioxane or methyl tert-butyl ether; the nitrile solvent is preferably acetonitrile; the sulfoxide solvent is preferably dimethyl sulfoxide; (2) The deuterated reagent is deuterated water, R 8 -O 2 H or R 8 and R 9 Independently for C 1-4 Alkyl or C 6-14 Aryl; Preferably, the deuterated reagent is deuterated water, MeO 2 H, EtO 2 H、iPrO 2 H or MeCO2 2 H; (3) The molar ratio of the deuterated reagent to the compound containing fragment I is (10-30):1, for example 20:1; (4) The tritiated reagent is tritiated water, R 10 -O 3 H or R 10 and R 11 Independently for C 1-4 Alkyl or C 6-14 Aryl; Preferably, the tritiated reagent is tritiated water; (5) The molar ratio of the amount of the tritiated reagent to the compound containing fragment I is (10-30):1, for example 20:1; (6) In the method for preparing the deuterated aldehyde compound, the reagents for the reduction reaction are the aprotic solvent, the phenol catalyst, the base, the additive, the compound containing fragment I, the hydrogen source and the deuterated reagent; (7) In the method for preparing the tritiated aldehyde compound, the reagents for the reduction reaction are the aprotic solvent, the phenol catalyst, the base, the additive, the compound containing fragment I, the hydrogen source and the tritiated reagent.

10. The method for preparing a deuterated or tritiated aldehyde compound according to claim 8 or 9, characterized in that: The preparation method of the deuterated or tritiated aldehyde compound is the following method 1, method 2 or method 3; Method 1: In an aprotic solvent, in the presence of a phenol catalyst, a base, an additive and light, a compound as shown in Formula IA and a hydrogen source are subjected to a reduction reaction in the presence of a deuterated reagent or a tritium reagent to obtain a compound as shown in Formula III-A; Method 2: In an aprotic solvent, in the presence of a phenol catalyst, a base, an additive and light, in the presence of a deuterated reagent or a tritium reagent, a compound as shown in Formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula III-B; Method 3: In an aprotic solvent, in the presence of a phenol catalyst, a base, an additive and light, in the presence of a deuterated reagent or a tritium reagent, a compound as shown in Formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula III-C; In method 1, method 2 and method 3, the aprotic solvent is as described in claim 8 or 9; the phenol catalyst, base, additive, light and hydrogen source are as described in any one of claims 1-3; the compound shown in formula IA, the compound shown in formula IB and the compound shown in formula IC are as described in any one of claims 4-7; the reaction temperature of the reduction reaction is as described in claim 2.

11. A method for preparing an alcohol compound, characterized in that: The method comprises the following steps: in a solvent, under the conditions of a phenol catalyst, a base and light, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment IV; Wherein, the fragment I is The fragment IV is The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment IV; The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene in the fragment I is directly connected; the carbonyl in the fragment I is not connected to N, O and S; The solvent, phenol catalyst, base, light and hydrogen source are as described in any one of claims 1-3.

12. The method for preparing an alcohol compound according to claim 11, characterized in that: The preparation method of the alcohol compound meets one or both of the following conditions: (1) The preparation method of the alcohol compound is the following method 1, method 2 or method 3; Method 1: In a solvent, under the conditions of phenol catalyst, base and light, a compound as shown in Formula IA and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula IV-A; Method 2: In a solvent, under the conditions of phenol catalyst, base and light, the compound represented by formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by formula IV-B; Method 3: In a solvent, under the conditions of phenol catalyst, base and light, the compound represented by formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by formula IV-C; The solvent, phenol catalyst, base, light and hydrogen source are as described in any one of claims 1-3; the compound of formula IA, the compound of formula IB and the compound of formula IC are as described in any one of claims 4-7; the reaction temperature of the reduction reaction is as described in claim 2; (2) In the method for preparing the alcohol compound, the reagents for the reduction reaction are the solvent, the phenol catalyst, the base, the compound containing fragment I and the hydrogen source.

13. A method for preparing a deuterated or tritiated alcohol compound, characterized in that: The method comprises the following steps: in an aprotic solvent, under the conditions of phenol catalyst, base and light, in the presence of a deuterated reagent or a tritium reagent, subjecting a compound containing fragment I to a reduction reaction with a hydrogen source to obtain a compound containing fragment V; Wherein, the fragment I is The fragment V is The carbon atom marked with "*" in the fragment I corresponds to the carbon atom marked with "*" in the fragment V; The fragment I does not react with -CH2-aryl-, -CH2-CH=CH2- and The methylene in the fragment I is directly connected; the carbonyl in the fragment I is not connected to N, O and S; The phenol catalyst, base, light and hydrogen source are as described in any one of claims 1 to 3, and the aprotic solvent, deuterated reagent and tritiated reagent are as described in claim 8 or 9.

14. The method for preparing a deuterated or tritiated alcohol compound according to claim 13, characterized in that: The preparation method of the deuterated or tritiated alcohol compound meets one or more of the following conditions: (1) The method for preparing the deuterated or tritiated alcohol compound is the following method 1, method 2 or method 3; Method 1: In an aprotic solvent, in the presence of a phenol catalyst, a base and light, a compound represented by Formula IA and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by Formula VA; Method 2: In an aprotic solvent, in the presence of a phenol catalyst, a base and light, in the presence of a deuterated reagent or a tritiated reagent, a compound as shown in Formula IB and a hydrogen source are subjected to a reduction reaction to obtain a compound as shown in Formula III-B; Method 3: In an aprotic solvent, in the presence of a phenol catalyst, a base and light, in the presence of a deuterated reagent or a tritiated reagent, a compound represented by formula IC and a hydrogen source are subjected to a reduction reaction to obtain a compound represented by formula VC; In method 1, method 2 and method 3, the phenol catalyst, base, light and hydrogen source are as described in any one of claims 1-3; the aprotic solvent, deuterated reagent and tritium reagent are as described in claim 8 or 9; the compound shown in formula IA, the compound shown in formula IB and the compound shown in formula IC are as described in any one of claims 4-7; the temperature of the reduction reaction is as described in claim 2; (2) In the preparation method of the deuterated alcohol compound, the reagents for the reduction reaction are the aprotic solvent, the phenol catalyst, the base, the compound containing fragment I, the hydrogen source and the deuterated reagent; (3) In the method for preparing the tritiated alcohol compound, the reagents for the reduction reaction are the aprotic solvent, the phenol catalyst, the base, the compound containing fragment I, the hydrogen source and the tritiated reagent.

15. Use of a phenol catalyst as a reagent for converting an ester compound into an aldehyde or alcohol compound, wherein the phenol catalyst is as described in any one of claims 1 to 3.

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