Process for the preparation of deuterated compounds by a wurtz-type reduction reaction under transition metal-free conditions and deuterated compounds obtained by this process

Abstract

The application discloses a method for preparing a deuterated compound through a boron-type reduction reaction under a transition metal-free condition and the deuterated compound obtained through the method. The method comprises the following steps: under the protection of an inert atmosphere and under normal temperature and pressure, de-aromatic deuterization is performed on (hetero)arene through an electro-optical catalysis method in the presence of a deuterated reagent, so that the deuterated compound is obtained. The method directly reduces an organic photocatalyst which is independent of a transition metal into a corresponding anion radical through an electro-optical catalysis synthesis technology, and the anion radical has strong reduction capacity after being excited by light, so that boron-type reduction deuterization of inert (hetero)arene is realized. The method is more moderate, has fewer side reactions, and has high yield of a target product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functionalization of aromatic compounds. More particularly, it relates to a method for preparing deuterated compounds by primary Birch-type reduction reaction under transition metal-free conditions and deuterated compounds obtained by the method. BACKGROUND

[0002] Due to the unique properties of deuterium atoms, deuterated chemicals play an important role in the fields of kinetic isotope effect research, drug discovery, material modification, and biochemical technology, and their synthesis has attracted much attention. As an important fossil resource extracted from coal and crude oil, aromatic hydrocarbon molecules are basic chemical building blocks in molecular science, and their reductive deuterium substitution reaction is therefore considered as a very attractive method to obtain various deuterated chemicals. However, the synthesis of reductive deuterated aromatic compounds has very limited options, and the few existing methods usually rely on transition metal catalysis (Nature 2020, 581, 288-293; Chem. Commun. 1985, 373-374; ACS. Catal. 2018, 8, 5276-5285; J. Am. Chem. Soc. 1988, 110, 7906-7907; J. Am. Chem. Soc. 1992, 114, 10358-10368.). The dangerous and expensive deuterium sources (such as D2, NaBD4), harsh reaction conditions and transition metal residues in these transition metal catalysis methods obviously limit their application in pharmaceutical and industrial fields. In view of the high practicability of aromatic structure and the growing demand for building deuterium-labeled compounds, it is imperative to develop a transition metal-free catalytic strategy for the selective reductive deuteriation of planar (hetero)arenes with high deuterium incorporation rate and mild conditions.

[0003] Due to the inherent aromatic stabilization energy of aromatic compounds, transition metal-free catalytic strategies face the following great challenges: (1) the reduction potential of (hetero)arenes is high; (2) side reactions such as over-reduction are prone to occur; (3) site selectivity is difficult to control. SUMMARY

[0004] Based on the above problems, the purpose of the present application is to provide a method for preparing deuterated compounds by primary Birch-type reduction reaction under transition metal-free conditions and deuterated compounds obtained by the method, so as to solve the problem that the expensive and dangerous deuterium source, harsh reaction conditions and noble metal catalyst in the existing (hetero)arene deuterium addition reaction greatly limit the application range of the reaction.

[0005] To achieve the above purpose, the present application adopts the following technical solutions:

[0006] On the one hand, the present application provides a method for preparing deuterated compounds by primary Birch-type reduction reaction under transition metal-free conditions, which comprises the following steps:

[0007] Under the protection of an inert atmosphere and at room temperature and pressure, in the presence of a deuterated reagent, an electro-photocatalytic method is used to dearomatize (hetero) aromatic hydrocarbons to obtain the deuterated compound.

[0008] In the technical solution of the present invention, "normal temperature and normal pressure" means a temperature of 25°C and a pressure of 101.325KPa.

[0009] Furthermore, the inert atmosphere is argon.

[0010] Furthermore, in the preparation method, the materials used do not contain transition metal catalysts.

[0011] Furthermore, the raw materials for dearomatization of (hetero)aromatic hydrocarbons further include an electrolyte, a solvent and an optional photocatalyst.

[0012] It is understood that the deuterated reagent and (hetero)aromatic hydrocarbon are also part of the raw materials. In the technical solution of the present invention, the components in the raw materials are combined together to form a mixed solution.

[0013] Furthermore, the deuterated reagent is selected from one or more of deuterated water, deuterated methanol, deuterated ethanol and deuterated isopropanol. The deuterated reagent is environmentally friendly, inexpensive, and more suitable for industrial production.

[0014] Furthermore, the electro-photocatalytic reaction is to electrolyze the raw material under visible light irradiation.

[0015] Furthermore, the electrolysis of the raw material is carried out in an electrolytic cell equipped with a cathode and an anode.

[0016] Furthermore, the electrolysis method is constant current electrolysis.

[0017] Furthermore, the materials of the cathode and anode include but are not limited to a mixture of one or more of meshed glassy carbon, carbon rods, carbon cloth, nickel foam, platinum sheets, zinc sheets, magnesium sheets, etc.

[0018] Furthermore, the electrolytic cell is one of a single-tank, double-tank or MEA electrolytic cell.

[0019] Furthermore, the current of the constant current electrolysis is 0.1 mA-20 mA, and the electrolysis time is 1 h-200 h.

[0020] Preferably, the current of the constant current electrolysis includes but is not limited to 0.1 mA-10 mA, 0.1 mA-5 mA, 0.5 mA-10 mA, 0.5 mA-5 mA, 0.1 mA-1 mA, 0.5 mA-1 mA, 1 mA, etc. In this case, the reaction yield is higher.

[0021] Further, the electrolyte is selected from one or more of LiOTf, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, n Bu4NBF4, LiClO4, and LiBr.

[0022] The solvent in the present application is only to provide a solution environment for the reactants, and those skilled in the art are capable of selecting a suitable solvent, and the present application does not limit this. Further, the solvent is selected from one or more of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol dimethyl ether, and 1,4-dioxane.

[0023] Preferably, when the solvent is THF, the molar ratio of the deuterated reagent to the (hetero)arene is 1-100. In some examples, the molar ratio of the deuterated reagent to the (hetero)arene includes but is not limited to 45-100, 45-70, 45-60, 55-100, 55-70, 65-100, 49.8, 55.3, 66.4, 99.6, etc.

[0024] In the technical solution of the present application, the photocatalyst is optionally present. Wherein "optionally present" means that the photocatalyst can be present or absent. When the photocatalyst is present in the raw material system, it is directly reduced to an anion radical at the cathode, and the latter is excited by visible light to generate a strong reducing excited-state anion radical, thereby reducing the (hetero)arene to an anion radical and returning the photocatalyst to the ground state. When the photocatalyst is absent in the raw material system, the (hetero)arene is directly reduced at the cathode. Then, the (hetero)arene anion radical reacts with the deuterated reagent to generate a deuterated radical intermediate, which is further reduced by the (excited-state) photocatalyst anion radical and is deuterated by the deuterated reagent, and finally converted into a deuterated de-arylation product.

[0025] The photocatalyst in the present application can catalyze the reaction process as long as the reduction potential is appropriate, therefore, when using the photocatalyst, those skilled in the art are capable of selecting a suitable photocatalyst, and the present application does not limit this.

[0026] Further, the photocatalyst is selected from one or more of N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenediimide (PDI), 9-mesityl-10-methylacridine perchlorate (Mes-Acr + -ClO4 - ) and 9,10-dicyanoanthracene (DCA).

[0027] In the technical solution of the present application, the (hetero)arene includes heteroarene and arene. Further, the (hetero)arene has a structure as shown in any one of the following formulas:

[0028]

[0029] wherein:

[0030] In formula I-1, R1and R2are each independently selected from H, Me, Et, Ph, or CON(Et)2.

[0031] In formula I-2, R3, R4, and R5are each independently selected from H, Me, or F.

[0032] In formula I-3, R6, R7, R8, R9, and R 10 are each independently selected from H, Me, OMe, Ph, or F.

[0033] In formula I-4, R 11 , R 12 , R 13 , and R 14 are each independently selected from H, Me, OMe, Ph, F, or pyridyl.

[0034] In formula I-5, R 15 is independently selected from H or Me.

[0035] Further, in formula I-1, the reaction site for de-aromatic deuteration is at C9 and C10 positions.

[0036] Further, in formula I-2, the reaction site for de-aromatic deuteration is at C2 and C3 positions of indene.

[0037] Further, in formula I-3, the reaction site for de-aromatic deuteration is at C2 and C3 positions of indene.

[0038] Further, in formula I-4, the reaction site for de-aromatic deuteration is at C2 and C3 positions.

[0039] Further, in formula I-5, the reaction site for de-aromatic deuteration is at C2 and C3 positions.

[0040] Further, , the reaction site for de-aromatic deuteration is at C5 and C8 positions.

[0041] Further, , the reaction site for de-aromatic deuteration is at C1 and C2 positions.

[0042] Further, , the reaction site for de-aromatic deuteration is at C9 position.

[0043] Further, , the reaction site for de-aromatic deuteration is at C2 and C3 positions of benzofuran.

[0044] Further, In some embodiments, the de-aromatizing reaction site is C2 and C3 of the benzothiophene.

[0045] In some embodiments, the molar concentration of the photocatalyst in the feedstock is between zero and the saturation molar concentration, and includes zero; the molar concentration of the deuterated reagent in the feedstock is between zero and the saturation molar concentration, and does not include zero; the molar concentration of the (hetero)arene in the feedstock is between zero and the saturation molar concentration, and does not include zero; the molar concentration of the electrolyte in the feedstock is between zero and the saturation molar concentration, and does not include zero.

[0046] Further, in the feedstock, the concentration of the (hetero)arene is 0.001M-10M, the concentration of the deuterated reagent is 0.001M-10M, the concentration of the electrolyte is 0.001M-10M, the concentration of the photocatalyst is 5x10 -3 M-5x10 -5 M.

[0047] Preferably, in the feedstock, the concentration of the (hetero)arene includes but is not limited to 0.01M-10M, 0.01M-5M, 0.01M-1M, 0.01M-0.5M, 0.01M-0.1M, 0.01M-0.05M, 0.02M-10M, 0.02M-5M, 0.02M-1M, 0.02M-0.5M, 0.02M-0.1M, 0.02M-0.05M, 0.02M-0.03M, etc. In this case, the reaction yield is higher.

[0048] Preferably, in the feedstock, the concentration of the electrolyte includes but is not limited to 0.1M-10M, 0.1M-5M, 0.1M-1M, 0.1M-0.5M, 0.1M-0.2M, etc.

[0049] Preferably, in the feedstock, the concentration of the photocatalyst includes but is not limited to 1x10 -4 M-8x10 -4 M, 1x10 - 4 M-6x10 -4 M, 1x10 -4 M-5x10 -4 M, 2x10 -4 M-8x10 -4 M, 2x10 -4 M-6x10 -4 M, 2x10 -4 M-5x10 - 4 M, 4x10 -4 M-8x10 -4 M, 4x10-4 M-6 x 10 -4 M, 4 x 10 -4 M-5 x 10 -4 M, 4 x 10 -4 M-4.5 x 10 -4 M, etc.

[0050] Further, the electro-optical catalytic light source is selected from an LED lamp, simulated sunlight, or a xenon lamp.

[0051] Further, the wavelength of the simulated sunlight is λ > 400 nm.

[0052] The present application selects an economical, green, and safe deuterium reagent, does not need a transition metal catalyst, and realizes selective reductive deuterium addition of (hetero)arenes at room temperature and normal pressure by means of electro-optical catalysis technology, to synthesize high-value-added deuterated chemicals. The method has mild reaction conditions, can deuterate various (hetero)arene chemicals by inputting a lower constant current at room temperature and irradiating with visible light or sunlight, and no over-reduction deuterium addition side reactions occur. The method has the characteristics of simple reaction process, high efficiency, greenness, and economy, solves the problems of using dangerous and expensive deuterium sources, harsh reaction conditions, and low selectivity in existing deuterium addition reactions, embodies the potential application of the method in the production of deuterated chemicals, and is especially in the field of drugs.

[0053] In another aspect, the present application provides a deuterated compound prepared by the preparation method as described above.

[0054] The beneficial effects of the present application are as follows:

[0055] In the method of the present application, an organic photocatalyst independent of a transition metal is directly reduced to a corresponding anion radical by means of electro-optical catalysis synthesis technology, and the latter can have strong reducing power by being excited by light, so as to realize the primary Bichat type reductive deuterium addition of inert (hetero)arenes. The method has milder reaction, fewer side reactions, and high yield of target products. BRIEF DESCRIPTION OF DRAWINGS

[0056] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings.

[0057] Figure 1 showing the H NMR chart of 9,10-dideuterio-9,10-dihydroanthracene in Example 1. 1 H NMR chart.

[0058] Figure 2 showing the H NMR chart of 9,10-dideuterio-9,10-dihydroanthracene in Example 1. 13 C NMR chart.

[0059] Figure 3 showing the H NMR chart of 9,10-dideuterio-9,10-dihydroanthracene in Example 1.1 H NMR chart.

[0060] Figure 4 H NMR chart. 13 C NMR chart.

[0061] Figure 5 H NMR chart. 1 C NMR chart.

[0062] Figure 6 H NMR chart. 13 C NMR chart.

[0063] Figure 7 H NMR chart. 1 C NMR chart.

[0064] Figure 8 H NMR chart. 13 C NMR chart.

[0065] Figure 9 H NMR chart. 1 C NMR chart.

[0066] Figure 10 H NMR chart. 13 C NMR chart.

[0067] Figure 11 H NMR chart. 1 C NMR chart.

[0068] Figure 12 H NMR chart. 13 C NMR chart.

[0069] Figure 13 H NMR chart. 1 C NMR chart.

[0070] Figure 14The 2,3-dideutero-2-phenyl-2,3-dihydro-1-benzofuran in Example 25 is shown. 13 C NMR spectrum.

[0071] Figure 15 The following table shows the reaction of 8-({4-[4-(2,3-dideutero-2,3-dihydrobenzo[b]thien-4-yl)piperazin-1-yl]butyl}oxy)-1,2-dihydroquinolin-2-one in Example 29: 1 H NMR spectrum.

[0072] Figure 16 8-({4-[4-(2,3-dideuteroyl-2,3-dihydrobenzo[b]thien-4-yl)piperazin-1-yl]butyl}oxy)-1,2-dihydroquinolin-2-one in Example 29 13 C NMR spectrum. DETAILED DESCRIPTION

[0073] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the following detailed description is illustrative rather than restrictive and should not be used to limit the scope of protection of the present invention.

[0074] Example 1

[0075] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0076] 0.002 mmol of PDI photocatalyst, 0.1 mmol of anthracene, 90 μL of deuterated water, and 0.675 mmol of LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a mixed solvent of ultra-dry THF / DME (6:1) was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 7 hours using a current of 1 mA under 440 nm LED irradiation. After the reaction, the solution was separated by a chromatographic column. H NMR and C NMR spectra (e.g. Figure 1 and Figure 2 The product was identified by mass spectrometry as 9,10-dideuteryl-9,10-dihydroanthracene with a yield of 83% (80% D). No over-reduction deuterated by-products were generated in the reaction.

[0077] Example 2

[0078] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0079] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 9-methylanthracene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA for 8 hours at room temperature and atmospheric pressure under 440 nm LED illumination. After completion of the reaction, the reaction was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product as 9,10-dideuteryl-9-methyl-9,10-dihydroanthracene with a yield of 90% (85% D1, 78% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0080] Example 3

[0081] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0082] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-ethylanthracene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA under 440 nm LED illumination at room temperature and atmospheric pressure for 9 hours. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 9,10-dideuteryl-2-ethyl-9,10-dihydroanthracene in a 57% yield (82% D). No over-reduction deuterated byproducts were produced.

[0083] Example 4

[0084] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0085] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 9-phenylanthracene, 120 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA for 10 hours at room temperature and atmospheric pressure under 440 nm LED illumination. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 9,10-dideuteryl-9-phenyl-9,10-dihydroanthracene with a yield of 83% (85% D1, 90% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0086] Example 5

[0087] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0088] 0.002 mmol of PDI photocatalyst, 0.1 mmol of N,N-diethylanthracene-9-carboxamide, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 9 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H-NMR, C-NMR, and mass spectrometry confirmed the product as 9,10-dideuteryl-N,N-diethyl-9,10-dihydroanthracene-9-carboxamide in a 78% yield (74% D1, 94% D2). No over-reduction deuterated byproducts were produced.

[0089] Example 6

[0090] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0091] 0.002 mmol of PDI photocatalyst, 0.1 mmol of acridine, 90 μL of deuterated water, and 0.675 mmol of LiClO4 were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1 mA current under 440 nm LED illumination. After the reaction, the solution was separated by chromatographic column. H NMR and C NMR spectra (e.g.Figure 3 and Figure 4 The product was identified by mass spectrometry as 9-deuterated-9,10-dihydroacridine with a yield of 38% (84% D). No over-reduced deuterated by-products were generated in the reaction.

[0092] Example 7

[0093] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0094] 0.002 mmol of PDI photocatalyst, 0.1 mmol of Ersene, 120 μL of deuterated water, and 0.675 mmol of LiClO₄ were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 10 hours using a 1 mA current under 440 nm LED illumination. After the reaction, the solution was separated by chromatographic column. H NMR and C NMR spectra (e.g., Figure 5 and Figure 6 The product was identified by mass spectrometry as 1,2-dideutero-1,2-dihydrocyclopenta[3,2,1-ij]naphthalene with a yield of 48% (82% D). No over-reduction deuterated by-products were generated during the reaction.

[0095] Example 8

[0096] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0097] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 1,4-dimethoxynaphthalene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 9 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 1,4-dideuteryl-5,8-dimethoxy-1,4-dihydronaphthalene in a 63% yield (80% D). No over-reduction deuterated byproducts were produced.

[0098] Example 9

[0099] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0100] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-phenylindene, 180 μL of deuterated water, and 0.675 mmol of LiClO₄ were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 12 hours using a 1 mA current under 440 nm LED illumination. After the reaction, the solution was separated by chromatographic column. H NMR and C NMR spectra (e.g., Figure 7 and Figure 8 The product was identified by mass spectrometry as 1,2-dideuteryl-2-phenyl-2,3-dihydro-1H-indene with a yield of 85% (93% D1, 84% D2). No over-reduction deuterated by-products were generated in the reaction.

[0101] Example 10

[0102] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0103] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-(2-methylphenyl)-1H-indene, 180 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 12 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 1,2-dideuteryl-2-(2-methylphenyl)-2,3-dihydro-1H-indene with a yield of 72% (95% D1, 82% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0104] Example 11

[0105] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0106] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-(3-methylphenyl)-1H-indene, 180 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a 6:1 ultra-dry THF / DME mixture was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 20 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 1,2-dideuteryl-2-(3-methylphenyl)-2,3-dihydro-1H-indene with a yield of 85% (91% D1, 86% D2). No over-reduction deuterated by-products were generated in the reaction.

[0107] Example 12

[0108] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0109] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-(4-methylphenyl)-1H-indene, 180 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a 6:1 ultra-dry THF / DME mixture was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 16 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 1,2-dideuteryl-2-(4-methylphenyl)-2,3-dihydro-1H-indene with a yield of 60% (92% D1, 96% D2). No over-reduction deuterated by-products were generated in the reaction.

[0110] Example 13

[0111] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0112] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-(4-fluorophenyl)-1H-indene, 180 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 10 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, F NMR, and mass spectrometry confirmed the product to be 1,2-dideuteryl-2-(4-fluorophenyl)-2,3-dihydro-1H-indene with a yield of 75% (93% D1, 95% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0113] Example 14

[0114] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0115] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 3-phenyl-1H-indene, 100 μL of deuterated water, and 0.675 mmol of LiClO4 were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1 mA current under 440 nm LED illumination. After the reaction, the solution was separated by chromatographic column. H NMR and C NMR spectra (e.g. Figure 9 and Figure 10 The product was identified by mass spectrometry as 1,2-dideuteryl-1-phenyl-2,3-dihydro-1H-indene with a yield of 70% (86% D). No over-reduction deuterated by-products were generated in the reaction.

[0116] Example 15

[0117] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0118] PDI photocatalyst, 0.1 mmol 6-methoxy-3-phenyl-1H-indene, 180 μL deuterium water, 0.675 mmol LiClO4 in a single-compartment electrolytic cell equipped with a reticulated glassy carbon cathode (1.0 cm x 1.0 cm x 0.5 cm), a magnesium flake anode (1.0 cm x 1.0 cm x 0.2 cm), 4.50 mL of a mixture of super-dry THF / DME (6:1) was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed under 440 nm LED irradiation at room temperature and normal pressure using a 1 mA current for 12 hours. After the reaction was completed, the product was separated by column chromatography. The product was identified as 1,2-dideuterio-5-methoxy-1-phenyl-2,3-dihydro-1H-indene by 1H NMR, 13C NMR and mass spectrometry, and the yield was 63% (92% D1, 88% D2). No over-reduction deuterated by-products were generated in the reaction.

[0119] Example 16

[0120] A method for preparing deuterated compounds by Birch-type reduction reaction without transition metal, comprising the following steps:

[0121] PDI photocatalyst, 0.1 mmol 6-methoxy-3-phenyl-1H-indene, 180 μL deuterium water, 0.675 mmol LiClO4 in a single-compartment electrolytic cell equipped with a reticulated glassy carbon cathode (1.0 cm x 1.0 cm x 0.5 cm), a magnesium flake anode (1.0 cm x 1.0 cm x 0.2 cm), 4.50 mL of a mixture of super-dry THF / DME (6:1) was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed under 440 nm LED irradiation at room temperature and normal pressure using a 1 mA current for 12 hours. After the reaction was completed, the product was separated by column chromatography. The product was identified as 1,2-dideuterio-5-methoxy-1-phenyl-2,3-dihydro-1H-indene by 1H NMR, 13C NMR and mass spectrometry, and the yield was 63% (92% D1, 88% D2). No over-reduction deuterated by-products were generated in the reaction.

[0122] Example 17

[0123] A method for preparing deuterated compounds by Birch-type reduction reaction without transition metal, comprising the following steps:

[0124] PDI photocatalyst, 0.1 mmol 5-fluoro-3-phenyl-lH-indene, 180 μL deuterium water, 0.675 mmol LiClO4 in a single-compartment electrolytic cell equipped with a reticulated glassy carbon cathode (1.0 cm x 1.0 cm x 0.5 cm), a magnesium flake anode (1.0 cm x 1.0 cm x 0.2 cm), 4.50 mL of super-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed under 440 nm LED irradiation at room temperature and atmospheric pressure using a 1 mA current for 10 hours. After the reaction was completed, the product was separated by column chromatography. The product was identified as 1,2-dideuterio-6-fluoro-l-phenyl-2,3-dihydro-lH-indene by NMR hydrogen spectrum, carbon spectrum, fluorine spectrum and mass spectrum with a yield of 93% (90% D). No over-reduction deuterated by-products were generated in the reaction.

[0125] Example 18

[0126] A method for preparing deuterated compounds by Birch-type reduction reaction without transition metal, comprising the following steps:

[0127] PDI photocatalyst, 0.1 mmol 3-methyl-benzothiophene, 90 μL deuterium water, 0.675 mmol LiClO4 in a single-compartment electrolytic cell equipped with a reticulated glassy carbon cathode (1.0 cm x 1.0 cm x 0.5 cm), a magnesium flake anode (1.0 cm x 1.0 cm x 0.2 cm), 4.50 mL of super-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed under 440 nm LED irradiation at room temperature and atmospheric pressure using a 1 mA current for 9 hours. After the reaction was completed, the product was separated by column chromatography. The product was identified as 2,3-dideuterio-3-methyl-2,3-dihydrobenzo[b]thiophene by NMR hydrogen spectrum, carbon spectrum (as shown in Figure 11 and Figure 12 spectrum) and mass spectrum with a yield of 45% (85% D1, 88% D2). No over-reduction deuterated by-products were generated in the reaction.

[0128] Example 19

[0129] A method for preparing deuterated compounds by Birch-type reduction reaction without transition metal, comprising the following steps:

[0130] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 5-methylbenzothiophene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA under 440 nm LED illumination at room temperature and atmospheric pressure for 9 hours. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 2,3-dideuteryl-5-methyl-2,3-dihydrobenzo[b]thiophene with a yield of 43% (83% D1, 84% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0131] Example 20

[0132] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0133] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 5-methoxybenzothiophene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 9 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H-NMR, C-NMR, and mass spectrometry confirmed the product as 2,3-dideuteryl-5-methoxy-2,3-dihydrobenzo[b]thiophene in a 49% yield (93% D1, 82% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0134] Example 21

[0135] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0136] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 5-fluoro-benzothiophene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA for 9 hours at room temperature and atmospheric pressure under 440 nm LED illumination. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, F NMR, and mass spectrometry confirmed the product to be 2,3-dideuteryl-5-fluoro-2,3-dihydrobenzo[b]thiophene with a yield of 58% (84% D1, 90% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0137] Example 22

[0138] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0139] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 4-fluoro-benzothiophene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA under 440 nm LED illumination at room temperature and atmospheric pressure for 9 hours. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, F NMR, and mass spectrometry confirmed the product to be 2,3-dideuteryl-4-fluoro-2,3-dihydrobenzo[b]thiophene in a 57% yield (88% D1, 91% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0140] Example 23

[0141] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0142] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-phenyl-benzothiophene, 120 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed at 1 mA for 10 hours at room temperature and atmospheric pressure under 440 nm LED illumination. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 2,3-dideuteryl-2-phenyl-2,3-dihydrobenzo[b]thiophene with an 80% yield (88% D1, 95% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0143] Example 24

[0144] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0145] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-pyridyl-benzothiophene, 120 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 10 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product as 2-(2,3-dideuteryl-2,3-dihydrobenzo[b]thiophen-2-yl)pyridine in a 51% yield (93% D1, 81% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0146] Example 25

[0147] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0148] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-phenylbenzofuran, 120 μL of deuterated water, and 0.675 mmol of LiClO₄ were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 10 hours under 440 nm LED illumination using a current of 1 mA. After the reaction, the solution was separated by chromatographic column. H NMR and C NMR spectra (e.g., Figure 13 and Figure 14 The product was identified by mass spectrometry as 2,3-dideutero-2-phenyl-2,3-dihydro-1-benzofuran with a yield of 68% (95% D1, 82% D2). No over-reduction deuterated by-products were generated in the reaction.

[0149] Example 26

[0150] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0151] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 2-phenylindole, 180 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a 6:1 ultra-dry THF / DME mixture was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 10 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product as 2,3-dideuterio-2-phenyl-2,3-dihydro-1H-indole in a 65% yield (95% D1, 93% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0152] Example 27

[0153] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0154] 0.002 mmol of PDI photocatalyst, 0.1 mmol of N-methyl-2-phenyl-indole, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 9 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 2,3-dideuterio-2-phenyl-2,3-dihydro-1H-indole in a 41% yield (88% D1, 85% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0155] Example 28

[0156] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0157] 0.002 mmol of PDI photocatalyst, 0.1 mmol of 4,7-dimethylindene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a 6:1 ultra-dry THF / DME mixture was added and degassed with argon for 20 minutes. The solution was then electrolyzed under 440 nm LED light at room temperature and atmospheric pressure for 12 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product to be 1,2-dideuterio-4,7-dimethyl-2,3-dihydro-1H-indene with a yield of 28% (72% D1, 70% D2). No over-reduction deuterated byproducts were formed during the reaction.

[0158] Example 29

[0159] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0160] 0.002 mmol of PDI photocatalyst, 0.1 mmol of epiprazole, 100 μL of deuterated water, and 0.675 mmol of LiClO₄ were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of ultra-dry THF was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 12 hours under 440 nm LED illumination using a current of 1 mA. After the reaction, the solution was separated by chromatographic column. H NMR and C NMR spectra (e.g. Figure 15 and Figure 16 The product was identified by mass spectrometry as 8-({4-[4-(2,3-dideutero-2,3-dihydrobenzo[b]thien-4-yl)piperazin-1-yl]butyl}oxy)-1,2-dihydroquinolin-2-one with a yield of 80% (99% D1, 40% D2). No over-reduction deuterated byproducts were generated during the reaction.

[0161] Example 30

[0162] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0163] Weigh 0.002mmol Mes-Acr + -ClO4 - The photocatalyst, 0.1 mmol anthracene, 90 μL deuterated water, and 0.675 mmol LiClO4 were placed in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a mixed solvent of ultra-dry THF / DME (6:1) was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 7 hours using a current of 1 mA under 440 nm LED irradiation. After the reaction, 1,3,5-trimethoxybenzene was used as an internal standard. 1 H NMR analysis determined the yield of 9,10-dideuteryl-9,10-dihydroanthracene to be 8.5%. No over-reduction deuterated byproducts were generated during the reaction.

[0164] Example 31

[0165] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0166] 0.1 mmol of anthracene, 90 μL of deuterated water, and 0.675 mmol of LiClO4 were weighed into a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a 6:1 mixed solvent of ultra-dry THF / DME was added and degassed with argon for 20 minutes. The solution was then electrolyzed continuously at room temperature and atmospheric pressure for 7 hours using a 1 mA current under 440 nm LED illumination. After the reaction, 1,3,5-trimethoxybenzene was used as an internal standard. 1 H NMR analysis determined the yield of 9,10-dideuteryl-9,10-dihydroanthracene to be 16%. No over-reduction deuterated byproducts were generated during the reaction.

[0167] Example 32 (Simulated Sunlight Experiment)

[0168] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0169] 0.002 mmol of PDI photocatalyst, 0.1 mmol of anthracene, 90 μL of deuterated water, and 0.675 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a mesh glassy carbon cathode (1.0 cm × 1.0 cm × 0.5 cm) and a magnesium sheet anode (1.0 cm × 1.0 cm × 0.2 cm). 4.50 mL of a 6:1 ultra-dry THF / DME mixture was added and degassed with argon for 20 minutes. The solution was then electrolyzed under simulated solar light (λ > 400 nm) at room temperature and atmospheric pressure for 10 hours at 1 mA. After completion of the reaction, the product was separated by chromatographic column. H-NMR, C-NMR, and mass spectrometry confirmed the product as 9,10-dideuteryl-9,10-dihydroanthracene with a yield of 70% (80% D). No over-reduction deuterated byproducts were produced.

[0170] Example 33 (Gram-scale scale-up experiment of Example 1)

[0171] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0172] 0.16 mmol of PDI photocatalyst, 8.0 mmol of anthracene, 7.2 mL of deuterated water, and 42.8 mmol of LiClO₄ were placed in a single-cell electrolytic cell equipped with a meshed glassy carbon cathode (5.0 cm × 1.0 cm × 0.6 cm) and a magnesium sheet anode (5.0 cm × 5.0 cm × 0.2 cm). 322.0 mL of a 6:1 ultra-dry THF / DME mixture was added and degassed with argon for 60 minutes. The solution was then electrolyzed under 440 nm LED illumination at room temperature and atmospheric pressure for 165 hours at 2.5 mA. After completion of the reaction, the reaction was separated by chromatographic column. H NMR, C NMR, and mass spectrometry confirmed the product as 9,10-dideuteryl-9,10-dihydroanthracene in a 69% yield (79% D). No over-reduction deuterated byproducts were produced.

[0173] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions, characterized in that: The steps include: Under the protection of an inert atmosphere and at room temperature and pressure, in the presence of a deuterated reagent, an electrophotocatalytic method is used to dearomatize (hetero)aromatic hydrocarbons to obtain the deuterated compound; The raw materials for the dearomatization deuteration reaction also include an electrolyte, a solvent and a photocatalyst; The deuterated reagent is selected from one or more of deuterated water, deuterated methanol, deuterated ethanol and deuterated isopropanol; The electrolyte is selected from LiOTf, 1-ethyl-3-methylimidazoline bis(trifluoromethylsulfonyl)imide, n One or more of Bu4NBF4, LiClO4 and LiBr; The photocatalyst is selected from N , N' - one or more of bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide, 9-mesityl-10-methylacridine perchlorate, and 9,10-dicyanoanthracene; The (hetero)arene has a structure as shown in any one of the following formulae: (I-1), (I-2), (I-3), (I-4), (I-5), , , , sum ; in: In formula I-1, R1 and R2 are each independently selected from H, Me, Et, Ph or CON(Et)2; In formula I-2, R3, R4 and R5 are each independently selected from H, Me or F; In formula I-3, R6, R7, R8, R9 and R 10 Each independently selected from H, Me, OMe, Ph or F; In formula I-4, R 11 、R 12 、R 13 and R 14 are each independently selected from H, Me, OMe, Ph, F or pyridyl; In formula I-5, R 15 Independently selected from H or Me.

2. The method according to claim 1, characterized in that In the method, the materials used do not contain transition metal catalysts.

3. The method according to claim 1, characterized in that The electro-photocatalysis is to electrolyze the raw material under visible light irradiation.

4. The method according to claim 3, characterized in that The electrolysis method is constant current electrolysis, and the current of the constant current electrolysis is 0.1 mA-20 mA.

5. The method according to claim 1, wherein The solvent is selected from one or more of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane.

6. The method according to claim 1, characterized in that In the raw materials, the concentration of (hetero)aromatic hydrocarbon is 0.001 M-10 M, the concentration of deuterated reagent is 0.001 M-10 M, the concentration of electrolyte is 0.001 M-10 M, and the concentration of photocatalyst is 5×10 -3 M-5×10 -5 M.

7. The method according to claim 1 or 3, characterized in that The light source for electro-photocatalysis is selected from LED lamps, simulated sunlight or xenon lamps.

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