Synthesis method of beta-deuterated alcohol through photo-induced chromium catalysis

Abstract

The invention relates to a synthesis method of photo-induced chromium-catalyzed beta-deuterated alcohol, which comprises the following steps: taking alpha-deuterated alkyl sulfonium salt and aldehyde as reaction raw materials, taking chromium salt as a catalyst, adding Hantzsch ester, taking tetrahydrofuran as a reaction solvent, and stirring and reacting at room temperature for 12 hours under the irradiation of 400-410nm blue light. After the reaction is finished, a series of beta-deuterated alcohols with higher deuteration rate are obtained, the reaction conditions are mild, the operation is simple and convenient, a reliable experimental method is provided for synthesizing deuterated molecules, and the industrial application prospect is very good.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis of deuterated organic compounds, and in particular relates to a method for synthesizing light-induced chromium-catalyzed beta-deuterated alcohol. Background Art

[0002] As a stable non-radioactive isotope, deuterium has been widely used in nuclear magnetic resonance analysis, mechanism research, pharmaceutical and biochemical research and development. Since the US Food and Drug Administration (FDA) approved the first deuterated drug Austedo (deutertrabenazine) for the treatment of "chorea symptoms" associated with Huntington's disease in 2017, the synthesis of deuterated organic molecules has attracted much attention, and more and more reaction strategies for synthesizing deuterated organic molecules have been successfully developed. However, how to achieve regioselective deuteration reactions in the alkyl region has always been a difficult point in organic synthesis.

[0003] The synthesis of α-deuterated alcohols can be synthesized by deuterated reduction reaction of carbonyl compounds (Chem.Rev.2022,122,6634-6718) or by means of activation reaction strategy of oxygen atoms for ortho-carbon-hydrogen bonds (Chem.Sci.2022,13,8744-8751). However, there are few reports on the synthesis method of β-deuterated alcohols, so developing a synthesis method for preparing β-deuterated alcohol compounds has important practical value. We have developed a reaction system with mild reaction conditions and simple system, using easy-to-obtain α-deuterated alkyl sulfonium salts (Angew.Chem.Int.Ed.2024,63,e202409862) and aldehyde compounds as raw materials, and a synthesis method for rapidly synthesizing β-deuterated alcohols under the reaction conditions of photocatalysis and chromium metal co-catalysis. Summary of the invention

[0004] The purpose of the present invention is to provide a reaction strategy using photocatalysis and chromium salt synergistic catalysis to achieve a method for synthesizing β-deuterated alcohols. The reaction uses easily available α-deuterated alkyl sulfonium salts and aldehyde compounds as raw materials, activates Hantzsch ester (HE) and α-deuterated alkyl sulfonium salt to form an electron donor acceptor (EDA) complex, and combines chromium salt catalysis to achieve the addition reaction of deuterated alkyl fragments and aldehydes, and synthesizes a series of β-deuterated alcohols with a high deuteration rate. The reaction conditions are mild, the operation is simple, and the reaction has good industrial application prospects.

[0005] A method for synthesizing β-deuterated alcohol by light-induced chromium catalysis, the method comprising the following steps:

[0006] α-deuterated alkyl sulfonium salt, aldehyde, Hantzsch ester and CrCl2 catalyst are dispersed in an organic solvent and reacted at room temperature under light of a certain wavelength. After the reaction is completed, β-deuterated alcohol is obtained.

[0007] The structural formula of the α-deuterated alkyl sulfonium salt is: The structural formula of the aldehyde is: The structural formula of the Hantzsch ester is: The structural formula of the β-deuterated alcohol is:

[0008] The α-deuterated alkyl sulfonium salt is selected from any one or more of the following:

[0009]

[0010] The aldehyde is selected from any one or more of the following:

[0011]

[0012] In one embodiment of the present invention, the wavelength is selected from any one or more of the following: 400-410 nm, 410-420 nm, 440-450 nm, and preferably 400-410 nm.

[0013] In one embodiment of the present invention, the reaction time is 12 hours.

[0014] In one embodiment of the present invention, the molar ratio of the α-deuterated alkyl sulfonium salt, the aldehyde, and the Hantzsch ester is 1.5:1.

[0015] In one embodiment of the present invention, the amount of chromium catalyst used is 20 mol% relative to aldehyde.

[0016] In one embodiment of the present invention, the molar ratio of Hantzsch ester to aldehyde is 3:1.

[0017] In one embodiment of the present invention, the organic solvent is selected from any one or more of the following: tetrahydrofuran, acetonitrile, ethylene glycol dimethyl ether, dioxane and acetone. Tetrahydrofuran is preferred.

[0018] In one embodiment of the present invention, the reaction is carried out under N2 atmosphere.

[0019] In one embodiment of the present invention, the synthetic route of the reaction is as follows:

[0020]

[0021] In one embodiment of the present invention, the β-deuterated alcohol compound specifically includes the following structure:

[0022]

[0023] In one embodiment of the present invention, the method comprises the following specific steps:

[0024] Add CrCl2 to a reaction tube equipped with a stirrer in a glove box, take the reaction tube out of the glove box, and add α-deuterated alkyl sulfonium salt, Hantzsch ester, aldehyde and solvent tetrahydrofuran in sequence under N2 atmosphere, and stir at room temperature for 12 hours under 400-410nm blue light. After the reaction is completed, filter the reaction mixture with silica gel, rinse with ethyl acetate, combine the organic phases, remove the solvent with a rotary evaporator to obtain a crude product, separate the crude product by silica gel column chromatography, use petroleum ether and ethyl acetate as eluents, and finally obtain the target compound.

[0025] Beneficial effects:

[0026] The invention uses α-deuterated alkyl sulfonium salt and aldehyde compound as raw materials, chromium salt as catalyst, Hantzsch ester as reducing agent, tetrahydrofuran as reaction solvent, and reacts at room temperature for 12 hours under irradiation of 400-410nm blue light, and obtains β-deuterated alcohol compound after the reaction. The synthesis method of the invention has simple and easy-to-obtain catalyst and reaction raw materials, mild reaction conditions, good functional group compatibility, convenient operation, and good industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The schematic diagram of the synthesis method of the present invention is shown in FIG. DETAILED DESCRIPTION

[0028] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited to the scope of the embodiments.

[0029] Example 1

[0030] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 1 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 1 (isolation yield 82%) was obtained.

[0031]

[0032] 1 H NMR (600MHz, CDCl3) δ7.28 (td, J=7.5, 2.8Hz, 4H), 7.22-7.15 (m, 6H), 3.64 (dd, J=8.2, 4.1Hz, 1H), 2.78 (ddd, J=13.7, 9. 8, 5.6Hz, 1H), 2.65 (dddd, J=14.8, 13.5, 9.8, 6.7Hz, 3H), 1.82-1.70 (m, 3H), 1.66 (dt, 1=14.0, 7.6Hz, 1H), 1.36 (s, 1H). 13 C NMR (151MHz, CDCl3) δ142.29, 142.07, 128.38, 128.29, 125.80, 125.73, 71.07, 38.99, 36.50, 36.38, 36.26, 36.13, 35.78, 32.00, 27.18.

[0033] Example 2

[0034] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 2 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 2 (isolation yield 65%) was obtained.

[0035]

[0036] 1 H NMR (600MHz, CDCl3) δ7.28 (dd, J=8.3, 7.0Hz, 2H), 7.19 (dd, J=7.9, 1.8Hz, 3H), 3.37 (d, J=5.4Hz, 1 H), 2.69-2.58(m, 2H), 1.84-1.71(m, 4H), 1.69-1.60(m, 3H), 1.34-1.19(m, 4H), 1.18-0.96(m, 3H). 13 C NMR (151MHz, CDCl3) δ142.49, 128.38, 128.26, 125.67, 75.94, 43.55, 35.89, 32.87 (dd, J=37.6, 18.8Hz), 29.26, 27.65, 27.55, 26.52, 26.34, 26.17.

[0037] Example 3

[0038] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 3 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 3 (isolation yield 78%) was obtained.

[0039]

[0040] 1 H NMR (600MHz, CDCl3) δ7.38-7.30 (m, 4H), 7.30-7.25 (m, 3H), 7.21-7.11 (m, 3H), 4.68 (s, 1H), 2 .64(t, J=7.7Hz, 2H), 1.81(s, 1H), 1.76(dt,J=13.4, 7.8Hz, 1H), 1.61(dt,J=13.4, 7.8Hz, 1H). 13C NMR (151MHz, CDCl3) δ144.67, 142.23, 128.46, 128.39, 128.27, 127.55, 125.87, 125.72, 74.42, 37.81 (dd, J=38.5, 19.1Hz), 35.67, 27.36.

[0041] Example 4

[0042] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 4 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 4 (isolation yield 83%) was obtained.

[0043]

[0044] 1 H NMR (600MHz, CDCl3) δ7.28 (ddd, J=15.6, 7.9, 4.8Hz, 4H), 7.21-7.12 (m, 3H), 7.05-6.98 (m, 2H), 4.66 ( s, 1H), 2.63 (t, J=7.7Hz, 2H), 1.85 (s, 1H), 1.73 (dt, J=13.4, 7.8Hz, 1H), 1.59 (dd, J=14.4, 6.7Hz, 1H). 13 C NMR (151MHz, CDCl3) δ162.14 (d, J=245.2Hz), 142.10, 140.36 (d, J=3.1Hz), 128.36, 128.30, 127. 49 (d, J=8.2Hz), 125.77, 115.23 (d, J=21.3Hz), 73.74, 37.75 (dd, J=38.3, 20.1Hz), 35.61, 27.27. 19 F NMR (565MHz, CDCl3) δ-115.11.

[0045] Example 5

[0046] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 5 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 5 (isolation yield 76%) was obtained.

[0047]

[0048] 1 H NMR (600MHz, CDCl3) δ7.30-7.25 (m, 4H), 7.20-7.13 (m, 4H), 7.06 (dd, J=5.0, 1.3Hz, 1H ), 4.78 (s, 1H), 2.64 (t, J=7.7Hz, 2H), 1.80-1.73 (m, 2H), 1.63 (dd, J=14.1, 7.1Hz, 1H). 13 C NMR (151MHz, CDCl3) δ146.17, 142.19, 128.39, 128.29, 126.14, 125.75, 125.59, 120.73, 70.41, 37.13 (dd, J=39.2, 20.4Hz), 35.62, 27.21.

[0049] Example 6

[0050] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 6 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 6 (isolation yield 55%) was obtained.

[0051]

[0052] 1 H NMR (600MHz, CDCl3) δ7.31-7.26 (m, 2H), 7.21-7.17 (m, 3H), 4.37 (d, J=5.1Hz, 1H), 2.67 (t, J=7.7Hz, 2H), 1.85-1.73 (m, 3H), 0.17 (s, 9H). 13 C NMR (151MHz, CDCl3) δ142.07, 128.39, 128.31, 125.78, 106.63, 89.55, 62.63, 36.38 (dd, J=37.8, 19.0Hz), 35.31, 26.58, -0.14.

[0053] Example 7

[0054] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 7 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 7 (isolation yield 42%) was obtained.

[0055]

[0056] 1 H NMR (600MHz, CDCl3) δ7.34 (t, J=7.6Hz, 2H), 7.31-7.25 (m, 4H), 7.25-7.16 (m, 4H), 6.49 (s, 1H), 4.19 (s, 1H ), 2.68 (t, J=7.7Hz, 2H), 1.84 (d, J=1.4Hz, 3H), 1.76 (dt, J=14.9, 7.7Hz, 1H), 1.65 (dd, J=14.5, 6.7Hz, 1H). 13 C NMR (151MHz, CDCl3) δ142.29, 140.19, 137.49, 128.95, 128.40, 128.30, 128.10, 1 26.44, 125.90, 125.74, 77.92, 35.73, 33.82 (dd, J=37.9, 19.7Hz), 27.37, 13.09.

[0057] Example 8

[0058] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 8 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 8 (isolation yield 58%) was obtained.

[0059]

[0060] 1 H NMR (600MHz, CDCl3) δ7.67 (dd, J=8.6, 1.9Hz, 2H), 7.47 (dt, J=8.9, 2.2Hz, 2H), 7.32-7.23 (m, 4H) , 7.16 (ddd, J=19.1, 7.4, 4.0Hz, 3H), 7.09-7.01 (m, 3H), 6.91 (dd, J=9.0, 3.1Hz, 1H), 6.71 (dd, J= 9.0, 2.6Hz, 1H), 4.64 (s, 1H), 3.91 (d, J=2.3Hz, 2H), 3.84 (d, J=2.0Hz, 3H), 2.62 (t, J=7.8Hz, 2H) , 2.46 (d, J=2.1Hz, 3H), 2.04 (s, 1H), 1.73 (dt, J=13.1, 7.8Hz, 1H), 1.59 (dt, J=13.2, 7.8Hz, 1H). 13 C NMR (151MHz, CDCl3) δ169.29, 168.26, 156.06, 149.83, 142.44, 142.08, 139.28, 136.15, 133.75, 131.14, 130.79, 130.44, 129.09, 128.33, 128.24, 126.86, 125.70, 121.25, 114.97, 111.94, 111.73, 101.19, 73.66, 55.67, 37.79 (dd, J=38.4, 18.5Hz), 35.57, 30.48, 27.22, 13.37.

[0061] Example 9

[0062] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 2 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 1 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 9 (isolation yield 76%) was obtained.

[0063]

[0064] 1 H NMR (600MHz, CDCl3) δ7.29 (t, J=7.6Hz, 2H), 7.24-7.16 (m, 3H), 3.62 (dd, J=8.1, 4.1Hz, 1H), 2.74 (dddd, J=74 .5, 13.7, 9.9, 6.1Hz, 2H), 1.85-1.69 (m, 2H), 1.42 (p, J=7.6Hz, 1H), 1.38-1.23 (m, 6H), 0.89 (t, J=6.9Hz, 3H). 13 C NMR (151MHz, CDCl3) δ142.22, 128.39, 128.37, 125.76, 71.31, 39.02, 36.66 (dd, J=37.9, 19.0Hz), 32.05, 31.81, 25.06, 22.62, 14.01.

[0065] Example 10

[0066] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 3 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 1 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 10 (isolation yield 61%) was obtained.

[0067]

[0068] 1 H NMR (600MHz, CDCl3) δ7.42-7.38 (m, 2H), 7.29 (t, J=7.6Hz, 2H), 7.22-7.17 (m, 3H), 7.08-7. 04 (m, 2H), 3.64 (dd, J=7.9, 4.4Hz, 1H), 2.83-2.59 (m, 4H), 1.87-1.74 (m, 2H), 1.41 (s, 1H). 13 C NMR (151MHz ， CDCl3) δ 141.85, 140.98, 131.42, 130.15, 128.44, 128.36, 125.89, 119.52, 70.46, 39.15, 38.09 (dd, J=38.3, 19.6Hz), 32.00, 31.20.

[0069] Embodiment 11

[0070] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 4 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 1 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 11 (isolation yield 57%) was obtained.

[0071]

[0072] 1 H NMR (600MHz, CDCl3) δ7.33-7.27(m, 2H), 7.23-7.18(m, 3H), 7.13(dd, J=5.1, 1.2Hz, 1H), 6.93 (dd, J=5.2, 3.4Hz, 1H), 6.80 (dd, J=3.3, 1.3Hz, 1H), 3.70 (d t, J=8.0, 3.7Hz, 1H), 3.04-2.89 (m, 2H), 2.80 (ddd, J=13.8, 9.6, 6.0Hz, 1H), 2.69 (ddd, J=13.8, 9.6, 6.7Hz, 1H), 1.87-1.76 (m, 2H), 1.46 (d, J=4.2Hz, 1H). 13 C NMR (151MHz, CDCl3) δ144.83, 141.90, 128.42, 128.36, 126.76, 125.86, 124.20, 123.04, 70.42, 39.12, 38.61 (dd, J=38.5, 19.7Hz), 32.00, 25.92.

[0073] Example 12

[0074] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkyl sulfonium salt 5 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 1 (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was filtered through silica gel, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by rotary evaporator to obtain a crude product, which was separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally the compound of formula 12 (isolation yield 65%) was obtained.

[0075]

[0076] 1H NMR (600MHz, CDCl3) δ7.29 (t, J=7.6Hz, 2H), 7.22-7.17 (m, 3H), 3.82 (t, J=6.2Hz, 1H), 2.76 (dd d, J=13.7, 9.5, 6.1Hz, 1H), 2.68 (ddd, J=13.8, 9.4, 6.9Hz, 1H), 1.84-1.71 (m, 2H), 1.36 (s, 1H). 13 C NMR (151MHz, CDCl3) δ142.04, 128.39, 128.38, 125.81, 67.38, 40.77, 32.11, 29.68.

[0077] Example 13 Synthesis of target product using different solvents

[0078] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkylsulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), aldehyde 1 (0.2mmol, 1equiv), solvent (1.0mL) were added in sequence, irradiated under 400-410nm blue light, and stirred at room temperature for 12h. The reaction results are shown in Table 1.

[0079] Table 1 Synthesis results of different solvents

[0080] Solvents The NMR yield of the compound of formula 1 Tetrahydrofuran 90％ Acetonitrile 53％ Ethylene glycol dimethyl ether 71％ Dioxane 60％ acetone 70％

[0081] Example 14 Synthesis of target product by illumination with different wavelengths

[0082] In a reaction tube equipped with a stirrer, under N2 atmosphere, catalyst CrCl2 (0.04mmol, 20mol%), α-deuterated alkylsulfonium salt 1 (0.3mmol, 1.5equiv), Hantzsch ester (HE) (0.6mmol, 3.0equiv), phenylpropanal (0.2mmol, 1equiv), tetrahydrofuran solvent (1.0mL) were added in sequence, irradiated under blue light of different wavelengths, and stirred at room temperature for 12h. The reaction results are shown in Table 2.

[0083] Table 2 Synthesis results of different wavelengths of light

[0084] wavelength The NMR yield of the compound of formula 1 400-410nm 90％ 410-420nm 83％ 440-450nm 70％ 490-500am 0 No light 0

[0085] Although the present invention has been described by the specific embodiments above, it should not be construed as being limited thereto; rather, the present invention encompasses the general aspects disclosed above. Various modifications and various embodiments are possible without departing from the spirit and scope of the present invention.

Claims

1. A method for synthesizing light-induced chromium-catalyzed β-deuterated alcohols, characterized in that: The method comprises the following steps: α-deuterated alkyl sulfonium salt, aldehyde, Hantzsch ester and CrCl2 catalyst are dispersed in an organic solvent and reacted at room temperature under light of a certain wavelength. After the reaction is completed, β-deuterated alcohol is obtained. The structural formula of the α-deuterated alkyl sulfonium salt is: The structural formula of the aldehyde is: The structural formula of the Hantzsch ester is: The structural formula of the β-deuterated alcohol is: The α-deuterated alkyl sulfonium salt is selected from any one or more of the following: The aldehyde is selected from any one or more of the following: The organic solvent is selected from any one or more of the following: tetrahydrofuran, acetonitrile, ethylene glycol dimethyl ether, dioxane and acetone. The wavelength is selected from any one or more of the following: 400-410nm, 410-420nm, 440-450nm.

2. The method for synthesizing light-induced chromium-catalyzed β-deuterated alcohol according to claim 1, characterized in that: The molar ratio of the α-deuterated alkyl sulfonium salt reagent to the aldehyde is 1.5:

1.

3. The method for synthesizing light-induced chromium-catalyzed β-deuterated alcohol according to claim 1, characterized in that: The amount of CrCl2 used relative to the aldehyde reagent is 20 mol%.

4. The method for synthesizing light-induced chromium-catalyzed β-deuterated alcohol according to claim 1, characterized in that: The molar ratio of the Hantzsch ester to the aldehyde is 3:1.

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