A process for the preparation of a vicinal diol compound

Abstract

The present application relates to a kind of preparation method of vicinal diol compound, which comprises the following steps: in non-aqueous solvent, formula (I) compound and reducing agent are reacted under light condition, to obtain the vicinal diol compound shown in formula (II);The reducing agent is formic acid or formate;The wavelength of the light is less than 390nm;Its reaction formula is as follows.The preparation method of the present application does not need transition metal catalyst, also does not need other special catalyst and special additive, and the aldehyde ketone substrate can be reacted with formic acid or formate in solvent by specific wavelength of light, to obtain corresponding vicinal diol compound with high yield, its reaction condition is mild, has wide substrate applicability, and green and environmental protection, simple and practical operation method, provides an effective synthesis strategy for the synthesis of shikimic alcohol compound.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for preparing a vicinal diol compound. Background Technology

[0002] Developing a mild, efficient, and economical method for constructing carbon-carbon bonds from inexpensive and readily available raw materials has always been a hot topic in synthetic chemistry. The traditional pinacol coupling reaction is one of the most important reactions for constructing carbon-carbon bonds. The pinacol coupling reaction is an organic reaction in which the carbonyl group of an aldehyde or ketone molecule undergoes a free radical reaction in the presence of an electron donor, forming a new carbon-carbon covalent bond. The reaction product is a vicinal diol. Pinacol coupling reactions usually occur primarily through homo-molecular coupling, but cross-coupling reactions between different molecules can also occur. The resulting pinacol compounds (vicinal diols) are key intermediates in the preparation of pharmaceuticals, pesticides, and polyesters.

[0003] Traditional pinacol coupling processes require metal catalysts and stoichiometric metal reducing agents such as Mg, Al, Zn, and Mn, and the reaction conditions are relatively harsh. These traditional methods generate large amounts of metal waste during production. In recent years, photocatalysis and electrochemistry have become research hotspots, and using them to obtain pinacol compounds has become a useful approach. However, both photocatalysis and electrochemistry methods require photocatalysts, reducing agents, and other special additives. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a new method for preparing vicinal diol compounds that is greener, more efficient, and easier to operate.

[0005] To achieve the above-mentioned objectives, the present invention includes the following technical solutions.

[0006] A method for preparing a vicinal diol compound includes the following steps:

[0007] In a non-aqueous solvent, the compound shown in formula (I) and a reducing agent react under light irradiation to obtain the vicinal diol compound shown in formula (II);

[0008] The reducing agent is formic acid or formate;

[0009] The wavelength of the light is less than 390 nm;

[0010] The reaction formula is as follows:

[0011]

[0012] Wherein, R1 is selected from: substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups;

[0013] R2 is selected from: H, alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; or the substituent in R1 is connected to R2 to form a carbocyclic or heterocyclic ring.

[0014] The method for preparing the vicinal diol compound of the present invention has the following beneficial effects:

[0015] 1. The method of the present invention does not require the addition of transition metal catalysts, nor any other special catalysts or special additives. Aldehydes or ketone substrates can react with formic acid or formate salts in a solvent under light of a specific wavelength to obtain the corresponding vicinal diol compounds in high yield.

[0016] 2. The method of the present invention has a very wide range of substrate applicability. Using various aryl ketones or aryl aldehydes as substrates, the corresponding vicinal diol compounds can be prepared in excellent or high yields.

[0017] 3. The method of the present invention produces no other byproducts besides carbon dioxide, has a high yield, high product purity, is easy to purify, and has a simple post-processing procedure; moreover, its operation method is simple and practical, the reaction conditions are mild, which is conducive to batch and large-scale reaction, and can generate pinacol compounds on a large scale, providing an efficient and simple synthetic strategy for the synthesis of pinacol compounds.

[0018] 4. The method of the present invention uses formate (potassium formate, sodium formate, cesium formate, etc.) which are widely available, inexpensive, easy to store and transport, and safe to operate as a reducing agent, without any other additives, and has low preparation cost.

[0019] 5. The method of the present invention preferably uses green alcohol compounds (such as ethanol) as solvents. The solvents can be recycled and reused, resulting in less waste and making it green and environmentally friendly. Detailed Implementation

[0020] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are merely illustrative of the present invention and should not be construed as limiting the invention.

[0021] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0022] The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, apparatus, product, or device that includes a series of steps is not limited to the steps or modules listed, but may optionally include steps not listed, or may optionally include other steps inherent to such process, method, product, or device.

[0023] In this invention, "multiple" refers to two or more. "And / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0024] To provide a green, efficient, and simple method for preparing vicinal diol compounds, one embodiment of the present invention provides a method for preparing vicinal diol compounds, which includes the following steps:

[0025] In a non-aqueous solvent, the compound of formula (I) and the reducing agent react under light to give the vicinal diol compound shown in formula (II);

[0026] The reducing agent is formic acid or formate;

[0027] The wavelength of the light is less than 390 nm;

[0028] The reaction formula is as follows:

[0029]

[0030] Wherein, R1 is selected from: substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups;

[0031] R2 is selected from: H, alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; or the substituent in R1 is connected to R2 to form a carbocyclic or heterocyclic ring.

[0032] This method requires no transition metal catalysts, nor any other special catalysts or additives. Aldehydes and ketones react with formic acid or formate salts in a solvent under light of a specific wavelength to obtain the corresponding vicinal diol compounds in high yields. The reaction conditions are mild, it has a wide range of substrate applicability, and it is environmentally friendly. The operation method is simple and practical, providing an effective synthetic strategy for the synthesis of pinacol compounds.

[0033] In some embodiments of the present invention, R1 is selected from: one or more C6-C molecules substituted or unsubstituted by R3. 10 Aryl, 1 or more R3-substituted or unsubstituted 5-10 heteroaryl groups;

[0034] Each R3 is independently selected from: H, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxycarbonyl, phenyl, naphthyl, phenoxy, naphthoxy, C1-C8 haloalkyl, halogen, or R3 connected to R2 to form a 5-7 membered carbon ring or heterocycle.

[0035] In some embodiments of the present invention, R1 is selected from: one or more R3-substituted or unsubstituted phenyl groups, one or more R3-substituted or unsubstituted naphthyl groups, one or more R3-substituted or unsubstituted thiophenyl groups, and one or more R3-substituted or unsubstituted furanyl groups.

[0036] In some embodiments of the present invention, each R3 is independently selected from: H, methyl, ethyl, isopropyl, isobutyl, tert-butyl, propyl, pentyl, hexyl, methoxy, phenoxy, methylthio, methoxyformyl, phenyl, trifluoromethyl, fluorine, chlorine, bromine; or R3 is connected to R2 to form a 6-membered carbon ring.

[0037] In some embodiments of the present invention, R2 is selected from: H, C1-C6 alkyl, one or more R3-substituted or unsubstituted C6-C6 alkyl groups. 10 Aryl, or 5-10 heteroaryl groups with one or more R3-substituted or unsubstituted groups.

[0038] In some embodiments of the present invention, R2 is selected from: H, C1-C3 alkyl, one or more R3-substituted or unsubstituted phenyl groups.

[0039] In some embodiments of the present invention, R2 is selected from: H, methyl, ethyl, propyl, phenyl, fluorophenyl, chlorophenyl, and methoxy-substituted phenyl.

[0040] In some embodiments of the present invention, the compound of formula (I) is selected from:

[0041]

[0042]

[0043] The vicinal diol compound represented by formula (II) is selected from:

[0044]

[0045]

[0046] The inventors have discovered that the method for preparing vicinal diol compounds of the present invention has a very wide range of substrate applicability, and high or excellent yields of vicinal diol products can be obtained using various aryl ketones or aldehydes and heteroaryl ketones or aldehydes as reaction substrates.

[0047] In some embodiments of the present invention, the reducing agent is selected from at least one of formic acid, potassium formate, sodium formate, cesium formate, calcium formate, and ammonium formate.

[0048] In some embodiments of the present invention, the reducing agent is selected from at least one of potassium formate, sodium formate, and cesium formate.

[0049] The inventors discovered that various formates or formic acids can achieve excellent reaction results and obtain the vicinal diol target product in high yield. In particular, potassium formate, sodium formate, and cesium formate can achieve product yields of over 99%, while the yield of ammonium formate is slightly lower than that of other formates.

[0050] In some embodiments of the present invention, the wavelength of the illumination is less than 380 nm.

[0051] In some embodiments of the present invention, the wavelength of the illumination is less than 370 nm.

[0052] In some embodiments of the present invention, the wavelength of the illumination is 300-390 nm.

[0053] In some embodiments of the present invention, the wavelength of the illumination is 350nm-380nm.

[0054] In some embodiments of the present invention, the wavelength of the illumination is 360nm-370nm.

[0055] In some embodiments of the present invention, the wavelength of the illumination is 363nm-367nm.

[0056] In some embodiments of the present invention, the wavelength of the illumination is 365 nm.

[0057] The inventors discovered that the target vicinal diol product can only be obtained efficiently under illumination of a specific wavelength of light. Without light or when the light wavelength is greater than 390 nm, the target vicinal diol product cannot be obtained.

[0058] In some embodiments of the present invention, the power of the illumination is 20W-40W, preferably 25W-35W.

[0059] In some embodiments of the present invention, the solvent is dimethyl sulfoxide and / or an alcohol solvent.

[0060] In some embodiments of the present invention, the solvent is selected from at least one of dimethyl sulfoxide, methanol, ethanol, isopropanol, n-propanol, and n-butanol.

[0061] The inventors discovered that the reaction solvent has a significant impact on the reaction results. When using DMSO and alcohols (MeOH, EtOH, i-PrOH, n-PrOH, n-BuOH, etc.) as reaction solvents, the reaction results are excellent, and the expected pinacol product can be obtained in a high yield of 99%. However, when water is used as the solvent, the expected vicinal diol target product cannot be obtained, and when THF and DMF are used as reaction solvents, the product yield will be greatly reduced.

[0062] In some embodiments of the present invention, the molar ratio of the compound of formula (I) to the reducing agent is 1:1-3.

[0063] In some embodiments of the present invention, the molar ratio of the compound of formula (I) to the reducing agent is 1:1.5-2.5.

[0064] In some embodiments of the present invention, the reaction temperature is 15°C-40°C.

[0065] In some embodiments of the present invention, the reaction temperature is 20°C-30°C.

[0066] In some embodiments of the present invention, the reaction time is 2 hours to 86 hours.

[0067] In some embodiments of the present invention, the reaction time is 8 hours to 72 hours.

[0068] The following are specific examples.

[0069] Example 1

[0070]

[0071] Reaction Procedure: Acetophenone (0.2 mmol), potassium formate (0.4 mmol), and ethanol (10 mL) were added sequentially to a 15 mL quartz tube equipped with a magnetic stir bar. The quartz tube was placed above a 30 W, 365 nm LED lamp, ensuring a distance of 8 mm between the quartz tube and the lamp substrate (avoiding contact with the lamp substrate). The reaction was stirred at room temperature (approximately 25 °C). The reaction was monitored using a TLC plate. After 12 hours of reaction, the reaction was stopped once the acetophenone substrate was completely reacted as detected by the TLC plate.

[0072] Post-processing: After the reaction was complete, the solvent was removed under reduced pressure, then 10 mL of water was added, and the reaction solution was extracted with ethyl acetate (10 mL × 3). The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness at 40 °C to obtain the crude product. The crude product was separated by column chromatography and evaporated at 40 °C to obtain the white solid target product 2,3-diphenyl-2,3-butanediol, with a yield of 99%.

[0073] Example 2

[0074]

[0075] Reaction steps: Acetophenone (0.166 mol, 1 equiv, 20 g), potassium formate (0.332 mol, 2 equiv), and ethanol (160 mL) were added sequentially to a 250 mL quartz round-bottom flask equipped with a magnetic stirrer. The reaction was carried out under stirring at room temperature (approximately 25 °C) and under 30 W, 365 nm LED illumination, ensuring a distance of 8 mm between the quartz round-bottom flask and the LED light plate (avoiding contact with the light plate). The reaction was monitored using a TLC plate, and the reaction was stopped when the acetophenone was completely reacted as detected by the TLC plate.

[0076] Post-processing: After the reaction was complete, the solvent was removed under reduced pressure, then 100 mL of water was added, and the reaction solution was extracted with ethyl acetate (100 mL × 3). The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness at 40 °C to obtain the crude product. The crude product was dissolved in 100 mL of ethyl acetate by heating and stirring to crystallize, yielding pure 2,3-diphenyl-2,3-butanediol with a yield of 99%.

[0077] Example 3

[0078]

[0079] Reaction steps: Using ethanol as solvent, prepare a mixed solution containing 0.01 mol acetophenone and 0.02 mol potassium formate per milliliter. At room temperature (approximately 25°C), the mixed solution is passed through a continuous flow reactor with a tube length of 14 m, a tube diameter of 2.0 mm, and a flow rate of 0.05 mL / s by a peristaltic pump under 30 W, 365 nm LED illumination.

[0080] Post-processing: The solvent was removed from the reaction solution under reduced pressure, an appropriate amount of water was added, and the reaction solution was extracted with an appropriate amount of ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness at 40°C to obtain the crude product. The crude product was dissolved in ethyl acetate by heating and stirred to crystallize, yielding pure 2,3-diphenyl-2,3-butanediol with a yield of 99%.

[0081] Example 4

[0082] The difference between this embodiment and Example 1 is that a different solvent was used (Table 1), while all other operations were the same as in Example 1. The solvents used in this embodiment include DMSO (dimethyl sulfoxide), H2O (water), THF (tetrahydrofuran), MeOH (methanol), EtOH (ethanol), DMF (dimethylformamide), i-PrOH (isopropanol), n-PrOH (n-propanol), and n-BuOH (n-butanol).

[0083] Reaction conditions: At 25°C, acetophenone 1a (0.2 mmol) was used as the substrate, potassium formate (0.4 mmol, 2 equiv) was used as the additive, 10 mL of solvent was used, and the reaction was carried out under 30 W, 365 nm ultraviolet irradiation for 12 h in air.

[0084] The reaction results showed that: when H2O was used as the reaction solvent, the expected product 3a was not obtained (2 in Table 1); when THF and DMF were used as reaction solvents, only a small amount of product 3a was generated (3-4 in Table 1); when DMSO and alcohols (MeOH, EtOH, i-PrOH, n-PrOH, n-BuOH) were used as reaction solvents, the reaction was very efficient, and the expected pinacol product 3a was obtained in 99% yield (1, 5-9 in Table 1).

[0085]

[0086] Table 1. Effect of reaction solvent on reaction effect

[0087]

[0088] Example 5

[0089] The difference between this embodiment and Example 1 is that different formates and other bases were used as additives (Table 2), while all other operations were the same as in Example 1. The formates used in this embodiment include HCO2Cs, HCO2Na, HCO2K, HCO2Ca, HCO2H, and HCO2NH4, and the other bases include KOH, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DABCO (triethylenediamine), and Et3N (triethylamine).

[0090] Reaction conditions: At 25°C, acetophenone 1a (0.2 mmol) was used as the substrate, formate or base (0.4 mmol, 2 equiv) was used as the additive, 10 mL DMSO was used as the solvent, and the reaction was carried out under 30 W, 365 nm ultraviolet irradiation for 12 h in air.

[0091] The results showed that, under the given reaction conditions, after 12 hours, using cesium formate as an additive, the expected pinacol product 3a was successfully obtained in 99% yield (Table 2, 1). However, when other bases, such as KOH, DBU, DABCO, and Et3N, were used as additives, the yield of product 3a was extremely low or nonexistent (Table 2, 2-6). Replacing cesium formate with other formate salts also resulted in excellent yields of pinacol product 3a (Table 2, 7-10); however, the yield decreased when ammonium formate was used as an additive (Table 2, 11). Therefore, various formate salts can yield the target product 3a in excellent yields. Considering cost, potassium formate, being inexpensive, is the preferred additive for the reaction.

[0092]

[0093] Table 2. Effects of formate and different bases on the reaction effect

[0094]

[0095] Example 6

[0096] The difference between this embodiment and Embodiment 1 is that different wavelengths of light sources were used (Table 3), while all other operations were the same as in Embodiment 1. This embodiment conducted the reaction under four light sources: 30W ultraviolet light (365nm), 30W violet light (395nm), 30W blue light (410nm), and 30W blue light (455nm).

[0097] Reaction conditions: At 25°C, acetophenone 1a (0.2 mmol) was used as the substrate, potassium formate (0.4 mmol, 2 equiv) was used as the additive, 10 mL of ethanol was used as the solvent, and the reaction was carried out under ultraviolet or blue light irradiation for 12 h under air conditions.

[0098] The results are shown in Table 3 below: when irradiated with ultraviolet light (365nm), pinacol product 3a was obtained in 99% yield; while when irradiated with ultraviolet light (395nm), blue light (410nm), and blue light (455nm), pinacol product 3a was not found.

[0099]

[0100] Table 3. Effects of reaction light source on reaction effect

[0101]

[0102] Example 7: Reactions of ketones with different substitutions

[0103] The difference between this embodiment and Example 1 is that the structure of reaction substrate 1 is different, while all other operations are the same as in Example 1.

[0104] Reaction conditions: The reaction was carried out at 25°C with ketone 1 (0.2 mmol) as the substrate, potassium formate (0.4 mmol, 2 eqiuv) as the additive, and 10 mL of ethanol as the solvent. The reaction was carried out under 30 W, 365 nm UV irradiation and in air for 12 h.

[0105] The results (Table 4) show that aliphatic ketones could not yield pinacol, while aromatic ketones yielded pinacol in high yields. Aromatic ketones with electron-donating groups such as methyl, isobutyl, tert-butyl, propyl, hexyl, methoxy, and phenoxy on the benzene ring all yielded pinacol in excellent yields (3b-3o). Aromatic ketones with electron-withdrawing groups such as fluorine, chlorine, bromine, and trifluoromethyl on the benzene ring also yielded pinacol in medium to high yields (3p-3t), with the yield decreasing when the electron-withdrawing group fluorine was in the ortho position (3r) and decreasing when chlorine and bromine were substituted (3s-3t). Pinacol with both electron-withdrawing and electron-donating groups on the benzene ring also yielded pinacol in high yields (3u-3v). When the benzene ring was converted to a naphthalene ring, product 3w was obtained in 70% yield. When the methyl group in acetophenone is replaced with a propyl group, product 3x can also be obtained in an excellent yield of 99%. In addition, substrate expansion of benzophenone compounds was carried out. When benzophenone compounds have electron-donating or electron-withdrawing groups, such as methyl, methoxy, fluorine, or chlorine substitution, pinacol products (3z-3ae) can be obtained in high or excellent yields.

[0106] Table 4. Substrate expansion for acetophenone compounds

[0107]

[0108]

[0109] The structural formulas of reaction substrate 1 are as follows:

[0110]

[0111] Example 8: Reactions of aldehydes with different substitutions

[0112] The difference between this embodiment and Example 1 is that the structure of the reaction substrate is different, but all other operations are the same as in Example 1.

[0113] Reaction conditions: At 25°C, aldehyde 4 (0.2 mmol) was used as the substrate, potassium formate (0.4 mmol, 2 equiv) was used as the additive, 10 mL of ethanol was used as the solvent, and the reaction was carried out under 30 W, 365 nm ultraviolet irradiation for 12 h in air.

[0114] The results (Table 5) show that: substrates with electron-donating groups at the ortho, meta, and para positions of aromatic aldehydes, such as those with methyl, tert-butyl, isobutyl, methoxy, or phenoxy groups, all yielded pinacol products in excellent yields (5b-5p, 5u). Substrates with electron-withdrawing groups at the meta and para positions of aromatic aldehydes, such as those with fluorine, chlorine, bromine, or trifluoromethyl groups, also yielded pinacol products in excellent yields (5q-5t, 99%), and substrates with a methylthio group at the para position also yielded pinacol products in 90% yield (5v).

[0115] Table 5 Substrate expansion for aldehydes

[0116]

[0117] The structural formulas of reaction substrate 4 are as follows:

[0118]

[0119] The structural characterization data of the pinacol compounds prepared in Examples 1-8 are as follows:

[0120] 127.25,127.16,127.09,127.07,127.00,126.91,78.91,78.66,25.11,24.94; HRMS(ESI,m / z):Calcd for C 16 H 18 O2Na[M+Na] + :265.125,Found:265.1195.

[0121] CDCl3): δ140.97,140.62,136.56,136.41,128.03,127.87,127.34,126.90,78.81,78.56,25.24,25.06,21.01,20.98; HRMS (ESI, m / z): Calcd for C 18 H 22 O2Na[[M+Na] + :293.1518,Found:293.1513.

[0122] 1.54(s,3H),1.45(s,4H). 13 C NMR(100 MHz,CDCl3):δ143.75,143.42,143.38,136.71,136.69,136.67,136.50,136.49,136.47,128.30,128.27,128.25,127.90,127.86,127.73,127.60,127.16,127.00,124.57,124.53,124.51,124.08,124.05,78.91,78.89,78.68,78.65,25.11,25.01,21.61,21.59;HRMS(ESI,m / z):Calcd for C 18 H 22 O2Na[[M+Na] + :293.1518,Found:293.1512.

[0123] CDCl3):(100MHz,CDCl3)δ147.54,147.44,141.35,141.00,127.31,126.90,125.33,125.22,78.79,78.51,33.65,33.64,25.19,25.12,24.07,24.03,23.99;HRMS(ESI,m / z):Calcd forC 22 H 30 O2Na[M+Na] + :349.2144,Found:349.2134.

[0124] 140.66,127.03,126.62,124.20,124.12,78.71,78.43,34.42,34.38,31.44,31.42,25.16;HRMS(ESI,m / z):Calcd for C 24 H 34 O2Na[M+Na] + :354.5340,Found:354.5322.

[0125] 6.2 Hz,4H),1.55(s,2H),1.47(s,4H),0.93(td,J=7.4,5.7 Hz,6H); 13C NMR(100 MHz,CDCl3):δ141.37,141.21,141.12,140.82,128.68,128.48,128.38,128.20,127.38,127.24,127.22,126.78,78.83,78.61,38.03,37.58,37.52,26.52,25.09,25.03,24.46,24.39,24.22,13.92,13.84,13.75;HRMS(ESI,m / z):Calcd for C 22 H 30 O2Na[M+Na] + :349.2144,Found:349.2134.

[0126] diol(3g);White solid(99%yield); 1 H NMR(400 MHz,CDCl3):δ7.10(dd,J=12.7,8.1 Hz,4H),7.06–6.96(m,4H),2.57(q,J=7.2 Hz,5H),2.29(d,J=6.6 Hz,1H),1.58(dq,J=12.9,6.1,5.4Hz,5H),1.53(s,2H),1.46(s,3H),1.39–1.24(m,13H),1.08–0.68(m,7H); 13 CNMR(100 MHz,CDCl3):δ141.62,141.59,141.46,141.43,141.12,140.83,128.53,127.31,127.26,127.17,126.85,126.81,78.85,78.63,35.53,35.48,31.81,31.78,31.42,31.39,31.36,29.04,28.97,25.08,25.03,25.01,22.68,14.14;HRMS(ESI,m / z):Calcd forC 27 H 40 O2Na[M+Na] + :419.2926,Found:419.2916.

[0127] 1.56(s,2H),1.49(s,4H); 13C NMR(100 MHz,CDCl3):δ141.39,141.05,135.29,135.16,135.08,135.04,128.74,128.64,128.44,128.34,124.91,124.42,78.75,78.50,25.29,25.19,19.93,19.90,19.35,19.31;HRMS(ESI,m / z):Calcd for C 20 H 26 O2Na[M+Na] + :321.1831,Found:321.1822.

[0128] 1.53(d,J=36.0 Hz,6H); 13 C NMR(100 MHz,CDCl3):δ158.54,158.45,136.10,135.77,128.57,128.14,112.56,112.41,78.72,78.50,77.36,77.25,77.05,76.73,55.21,25.18,25.01;HRMS(ESI,m / z):Calcd for C 18 H 22 O4Na[M+Na] + :325.1416,Found:325.1410.

[0129] 1H),6.77(d,J=7.6 Hz,5H),3.69(s,4H),3.65(s,3H),2.88(d,J=1.1 Hz,2H),1.54(s,3H),1.47(s,3H); 13 C NMR(100 MHz,CDCl3):δ158.79,158.60,145.63,145.25,128.17,128.02,120.05,119.46,113.46,113.08,112.66,112.53,78.86,78.86,78.62,55.15,55.13,25.08,24.95;HRMS(ESI,m / z):Calcd for C 18 H 22 O4Na[M+Na] + :325.1416,Found:325.1410.

[0130] Hz,2H),5.41(s,2H),3.40(s,6H),1.57(s,6H); 13 C NMR(100 MHz,CDCl3):δ157.89,132.09,129.80,128.25,120.21,111.22,55.35,24.49;HRMS(ESI,m / z):Calcd for C 18 H 22 O4Na[M+Na] + :325.1416,Found:325.1413.

[0131] (100 MHz,CDCl3):δ166.98,148.36,129.03,128.56,128.46,127.43,127.08,78.83,52.11,24.75;HRMS(ESI,m / z):Calcd for C 20 H 22 O6Na[M+Na] + :381.1314,Found:381.1311.

[0132] (100 MHz,DMSO-d6):δ146.63,140.21,138.50,128.90,127.21,126.57,126.36,125.93,67.84,25.88;HRMS(ESI,m / z):Calcd for C 28 H 26 O2Na[M+Na] + :417.1831,Found:417.1830.

[0133] (s,2H),1.58(d,J=1.2 Hz,2H),1.48(d,J=1.3 Hz,4H). 13 C NMR(100 MHz,CDCl3):δ147.93,147.42,136.20,119.89,111.32,109.66,78.83,55.83,55.71,55.69,24.93.HRMS(ESI,m / z):Calcd for C 20 H 26 O6Na[M+Na] + :385.1627,Found:385.1620.

[0134] (m,4H),2.62(s,1H),2.44(s,1H),1.59(s,2H),1.50(s,3H); 13 C NMR(100 MHz,CDCl3):δ157.32,157.15,156.31,156.09,138.82,138.40,129.79,129.76,128.86,128.47,123.33,123.21,118.93,118.90,118.87,118.73,117.66,117.38,117.33,78.75,78.54,25.10,25.00;HRMS(ESI,m / z):Calcd for C 28 H 26 O4Na[M+Na] + :449.1729,Found:449.1720.

[0135] 1H),2.40(s,1H),1.55(s,3H),1.50(s,4H); 13 C NMR(100 MHz,CDCl3):δ147.71,147.15,147.13,130.03,129.71,129.51,129.38,129.19,129.06,127.75,127.47,125.55,125.51,124.28,124.24,124.20,124.19,124.15,124.11,122.84,122.80,78.61,78.29,25.10,24.72;HRMS(ESI,m / z):Calcd for C 18 H 16 F6O2Na[M+Na] + :401.0952,Found:401.0922.

[0136] 2H),1.47(s,4H); 13 C NMR(100 MHz,CDCl3):δ163.24,163.15,160.80,160.70,139.50,139.47,139.12,139.09,129.11,129.03,128.72,128.64,114.08,114.01,113.87,113.80,78.59,78.34,25.15,24.89;HRMS(ESI,m / z):Calcd for C 16H 16 F2O2Na[M+Na]+:301.1016,Found:301.1011.

[0137] 3.08(s,1H),1.76(d,J=2.2 Hz,3H),1.64(t,J=2.2 Hz,4H). 13 C NMR(100 MHz,CDCl3):δ161.84,161.76,159.40,159.32,130.23,130.18,130.07,129.98,129.94,129.42,129.33,129.29,129.20,123.61,123.58,123.25,123.21,116.32,116.07,115.82,24.47,24.44,24.40,24.38,24.03,24.01,23.97,23.95;HRMS(ESI,m / z):Calcd for C 16 H 16 F2O2Na[M+Na] + :301.1016,Found:301.1011.

[0138] 7.9,1.5 Hz,1H),2.34(s,2H),1.56(s,3H),1.50(s,3H); 13 C NMR(100 MHz,CDCl3):δ145.87,145.32,133.52,133.43,128.53,128.41,127.69,127.44,127.39,127.19,125.56,125.21,78.54,78.22,25.11,24.77;HRMS(ESI,m / z):Calcd for C 16 H 16 Cl2O2Na[M+Na] + :333.0425,Found:333.0422.

[0139] Hz,2H),6.97–6.92(m,2H),2.21(s,4H),1.59–1.20(m,12H); 13C NMR(100 MHz,CDCl3):δ143.79,143.43,142.79,142.32,130.39,130.31,130.23,130.17,129.28,129.22,128.88,127.44,127.37,127.32,127.29,127.26,127.16,127.12,127.07,126.93,126.91,121.46,121.27,78.88,78.62,78.51,78.23,25.13,25.08,24.96,24.73;HRMS(ESI,m / z):Calcdfor C 16 H 16 Br2O2Na[M+Na] + :422.9395,Found:422.9350.

[0140] 3H),2.30(d,J=6.2 Hz,3H),1.56–1.50(m,2H),1.48–1.42(m,3H). 13 C NMR(100 MHz,CDCl3):δ142.27,141.80,134.68,134.56,133.27,133.11,130.08,129.75,127.83,127.70,126.31,125.89,25.14,24.87,20.16,20.13.HRMS(ESI,m / z):Calcd forC 18 H 20 Cl2O2Na[M+Na] + :361.0738,Found:361.0730.

[0141] 12.0,2.7 Hz,2H),6.34(dd,J=14.5,2.6 Hz,1H),3.71(d,J=0.9Hz,3H),3.67(d,J=0.9Hz,3H),2.95(s,2H),1.63(d,J=2.3 Hz,3H),1.55–1.47(m,3H). 13C NMR(100 MHz,CDCl3):δ162.21,162.16,160.26,160.14,160.01,159.77,159.72,130.71,130.65,130.51,130.45,122.26,122.22,122.15,122.11,109.33,109.31,109.00,108.98,102.04,101.75,101.46,79.47,79.43,79.37,79.33,55.50,55.46,24.50,24.48,24.44,24.42,24.08,24.01.HRMS(ESI,m / z):Calcd for C 18 H 20 F2O4Na[M+Na] + :361.1228,Found:361.1220.

[0142] 7.50–7.36(m,5H),7.27(dd,J=8.7,1.9 Hz,1H),2.91–2.64(m,1H),2.37(s,1H),1.68(s,2H),1.62(s,4H); 13 C NMR(100 MHz,CDCl3):δ141.54,141.02,132.69,132.56,132.48,132.39,128.45,128.34,128.32,127.81,127.38,126.73,126.48,125.99,125.91,125.90,125.82,125.53,79.27,78.91,26.71,25.60,25.30;HRMS(ESI,m / z):Calcd for C 24 H 22 O2Na[M+Na] + :365.1518,Found:365.1515.

[0143] CDCl3):δ141.75,140.85,128.16,127.48,127.29,127.08,126.80,126.61,81.68,37.80,37.34,16.86,16.69,14.51,14.49;HRMS(ESI,m / z):Calcd for C 20 H 26 O2Na[M+Na] +:321.1831,Found:321.1830.

[0144] 14.3,6.4,3.6 Hz,5H),1.57(q,J=3.8,3.1 Hz,1H),1.26(ddd,J=14.5,12.1,5.0 Hz,2H). 13 C NMR(100 MHz,CDCl3):δ140.56,138.39,129.09,129.06,128.87,127.22,126.41,36.47,31.16,20.10;HRMS(ESI,m / z):Calcd for C 20 H 22 O2Na[M+Na] + :317.1518,Found:317.1510.

[0145] 83.10.HRMS(ESI,m / z):Calcd for C 26 H 22 O2Na[M+Na] + :389.1518,Found:389.1511.

[0146] 128.59,128.54,128.50,128.48,128.22,128.06,128.03,127.23,127.20,126.80,126.73,82.96,20.97.HRMS(ESI,m / z):Calcd for C 28 H 26 O2Na[M+Na] + :417.1831,Found:417.1830.

[0147] (s,1H). 13 C NMR(100 MHz,CDCl3): 13 C NMR(101 MHz,CDCl3)δ143.89,143.67,130.51,130.48,130.43,130.40,128.41,128.35,127.51,127.37,127.24,114.17,113.96,82.80.HRMS(ESI,m / z):Calcd for C 26 H 20 F2O2Na[M+Na] +:425.1329,Found:425.1321.

[0148] 114.20,82.58.HRMS(ESI,m / z):Calcd for C 26 H 18 F4O2Na[M+Na] + :461.1141,Found:461.1131.

[0149] NMR(100 MHz,CDCl3):δ199.32,158.50,158.46,158.39,158.33,158.05,144.59,143.90,139.17,137.63,136.43,135.49,132.21,131.90,131.60,131.15,131.07,130.73,130.29,129.94,129.88,129.58,129.41,128.68,128.64,128.60,128.57,128.35,128.31,128.21,127.75,127.63,127.59,127.49,127.27,127.25,127.17,127.10,126.96,126.89,126.85,126.78,126.53,113.91,113.82,113.78,113.16,113.05,112.97,112.60,112.59,82.92,69.84,55.18,55.15,55.13;HRMS(ESI,m / z):Calcd for C 28 H 26 O4Na[M+Na] + :449.1729,Found:449.1722.

[0150] 133.04,132.86,130.19,130.15,130.11,128.67,128.61,128.51,128.39,128.36,128.29,127.63,127.57,127.53,127.48,127.43,127.38,82.78,82.75;HRMS(ESI,m / z):Calcd forC 26 H 20 Cl2O2Na[M+Na] + :457.0738,Found:457.0735.

[0151] 2.76–2.27(m,1H). 13 C NMR(100 MHz,CDCl3):δ139.93,139.76,128.43,128.16,128.10,128.01,128.00,127.88,127.14,127.01,79.10.HRMS(ESI,m / z):Calcd for C 14 H 14 O2Na[M+Na] + :237.0892,Found:237.0890.

[0152] NMR(100 MHz,CDCl3):δ137.79,137.48,137.05,137.03,128.99,128.83,127.07,126.89,78.79,21.18,21.15.HRMS(ESI,m / z):Calcd for C 16 H 18 O2Na[M+Na] + :265.2968,Found:265.2965.

[0153] (d,J=2.0 Hz,1H),6.78(dt,J=7.6,1.6 Hz,1H),4.59(s,1H),4.51(s,1H),2.82(s,2H),2.23(s,3H),2.18(s,3H); 13 C NMR(100 MHz,CDCl3):δ140.02,139.98,137.72,128.91,128.60,128.57,128.19,127.99,127.97,127.84,127.52,124.29,124.03,78.81,78.22,78.20,21.43,21.39.

[0154] NMR(100 MHz,CDCl3): 13 C NMR(101 MHz,CDCl3)δ151.21,150.75,137.34,130.07,126.93,126.50,125.44,125.36,125.08,34.59,34.51,31.37,31.35,26.94.

[0155]

[0156] 6.85–6.80(m,2H),5.07(s,1H),4.84(s,2H),3.01(s,2H),2.05(s,3H),1.56(s,6H); 13 C NMR(100 MHz,CDCl3):δ138.11,138.06,136.10,135.92,130.16,130.02,127.70,127.68,127.27,126.81,126.02,125.92,74.62,73.23,19.12,18.75.

[0157] 1H),4.51(d,J=1.9 Hz,1H),2.54(s,2H),2.16(s,6H),2.11(s,4H),2.10(s,4H); 13 C NMR(100MHz,CDCl3):δ137.80,137.70,136.65,136.58,136.32,136.03,129.67,129.37,128.39,127.99,124.69,124.36,78.40,78.21,19.81,19.76,19.51,19.46.

[0158]

[0159] NMR(100 MHz,CDCl3):δ138.14,137.79,135.62,135.28,133.27,132.60,130.13,130.09,128.57,128.43,127.62,127.19,74.38,73.80,21.11,21.07,18.86,18.34.

[0160] 1H),2.91(s,1H),2.37(d,J=7.2 Hz,2H),2.33(dd,J=7.2,1.5 Hz,2H),2.29–2.09(m,1H),1.74(dhept,J=16.5,6.8 Hz,2H),0.84–0.75(m,12H); 13C NMR(100 MHz,CDCl3):δ141.59,141.28,137.30,137.18,128.98,128.79,126.87,126.67,79.09,78.03,45.14,45.08,30.21,30.20,22.34,22.31,22.22.

[0161] 5.13(s,2H),4.93(s,4H),2.33(s,6H),2.28(s,12H),2.20(s,6H),1.71(s,12H); 13 C NMR(100MHz,CDCl3):δ137.33,137.19,136.10,135.67,135.44,135.18,130.92,127.08,126.87,126.65,126.57,77.36,77.04,76.73,74.43,73.57,21.04,20.99,19.18,18.80.

[0162] 5.14(s,1H),4.91(d,J=1.2 Hz,1H),3.00(s,2H),2.17(s,2H),2.01(d,J=6.3 Hz,6H),1.45(s,4H). 13 C NMR(100 MHz,CDCl3):δ138.27,137.96,136.60,136.54,134.91,134.57,129.40,129.19,128.58,125.57,125.41,125.20,124.92,124.45,74.82,73.97,26.95,20.78,20.65,14.76,14.26.

[0163] 2H),6.61–6.53(m,2H),4.65(d,J=1.3 Hz,1H),4.52–4.45(m,1H),3.59(dt,J=9.0,1.2Hz,6H),2.83–2.71(m,2H). 13 C NMR(100 MHz,CDCl3):δ159.46,159.36,141.63,141.45,129.16,129.11,119.50,119.33,113.89,113.87,113.64,112.39,112.32,78.84,55.23,55.20,55.18.

[0164] 7.17(m,8H),5.41(s,4H),4.71(d,J=2.1 Hz,4H); 13 C NMR(100MHz,DMSO-d6):δ142.26,140.44,138.89,129.35,128.29,127.69,126.94,126.05,77.54.

[0165] 5.07(s,1H),5.02(s,1H),3.80–3.70(m,8H),3.70–3.65(m,4H),3.20(s,2H). 13 C NMR(100MHz,CDCl3):δ152.34,146.84,146.63,134.33,133.89,133.85,124.03,124.00,123.92,120.14,120.10,111.94,111.89,73.80,73.78,73.69,60.83,60.82,60.69,55.77,55.73,18.81.

[0166] 6.86–6.76(m,1H),6.69(d,J=8.3 Hz,1H),4.63(s,1H),4.61(s,1H),3.85(s,3H),3.81(s,3H),2.92(s,1H),2.24(s,3H),2.18(s,3H),2.08(s,1H); 13 C NMR(100 MHz,CDCl3):δ199.10,157.35,157.17,131.84,131.34,130.13,129.42,129.13,128.21,127.34,127.30,126.31,125.83,125.50,110.25,109.75,109.47,78.49,62.65,55.39,55.36,55.31,55.27,16.29,16.22,16.12.

[0167] (m,6H),6.81–6.77(m,2H),4.71(s,1H),4.56(s,1H),2.96(s,1H),2.34(s,1H). 13 C NMR(100MHz,CDCl3): 13C NMR(101 MHz,DMSO)δ152.38,152.34,152.18,129.99,129.80,125.05,125.02,123.82,123.70,118.65,118.58,114.18,114.06,113.81,113.79,74.08,22.20.

[0168] 1H),4.73(s,1H),4.49(d,J=1.8 Hz,1H),2.97(s,2H); 13 C NMR(100 MHz,CDCl3):δ157.10,157.07,157.04,156.95,141.77,141.50,129.99,129.77,129.65,129.48,123.25,123.24,121.85,119.21,118.78,118.68,118.51,117.71,117.52,79.01.

[0169] 3.1,1.5 Hz,1H),4.65–4.60(m,1H),4.58(dd,J=3.2,1.3 Hz,1H); 13 C NMR(100 MHz,CDCl3):δ167.53,165.19,165.13,144.37,144.34,143.48,143.45,134.34,134.26,134.18,134.10,119.27,119.25,119.06,119.04,81.87,81.42.

[0170] 4.85(q,J=2.1 Hz,1H),4.66(q,J=2.7 Hz,1H),2.68(s,2H). 13 C NMR(100 MHz,CDCl3): 13 CNMR(101 MHz,CDCl3)δ163.91,161.47,142.22,142.15,142.06,141.99,129.76,129.68,129.60,122.65,122.62,122.59,115.14,115.11,114.93,114.90,114.06,113.92,113.84,113.70,78.40.

[0171] 4.68(d,J=2.6 Hz,1H),4.61(d,J=3.5 Hz,1H).

[0172] 130.84,130.63,130.52,130.30,130.19,129.98,128.00,127.33,127.27,125.35,125.29,125.27,125.23,125.20,125.16,125.12,125.09,125.05,125.01,122.65,122.59,78.37.

[0173] 2H),5.29(s,1H),5.07(s,1H),3.68(s,3H),3.66(s,3H),3.55(s,1H),3.20(s,1H). 13 C NMR(100MHz,CDCl3): 13 C NMR(100 MHz,CDCl3)δ156.97,156.92,128.66,128.56,128.50,128.44,128.27,128.24,120.46,110.25,110.22,74.35,73.42,73.41,55.27,55.23.HRMS(ESI,m / z):Calcd for C 16 H 18 O4Na[M+Na] + :297.1103,Found:297.1101.

[0174] 2.44(d,J=12.3 Hz,6H); 13 C NMR(100 MHz,DMSO-d6):δ140.53,139.53,136.53,136.38,128.47,128.39,128.31,125.67,125.61,125.54,77.50,77.04,15.45,15.29.

[0175] Hz,2H),6.75(dd,J=3.6,1.2 Hz,2H),5.05(s,1H),4.97(s,2H),3.02(s,1H),2.50(s,1H); 13C NMR (100MHz, CDCl3): δ142.91,142.54,126.64,126.61,126.03,125.86,125.65,125.42,74.96,74.44.

[0176] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0177] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing a vicinal diol compound, characterized in that, Includes the following steps: In a non-aqueous solvent, the compound of formula (I) and the reducing agent react under light irradiation to obtain the vicinal diol compound shown in formula (II); The reducing agent is selected from at least one of formic acid, potassium formate, sodium formate, cesium formate, calcium formate, and ammonium formate; The wavelength of the light is 360nm-370nm; The solvent is dimethyl sulfoxide and / or an alcohol solvent; The reaction formula is as follows: R1 is selected from: one or more R3-substituted or unsubstituted C6-C molecules. 10 Aryl, 1 or more R3-substituted or unsubstituted 5-10 heteroaryl groups; R2 is selected from: H, C1-C6 alkyl, one or more R3-substituted or unsubstituted C6-C 10 Aryl, 1 or more R3-substituted or unsubstituted 5-10 heteroaryl groups; Each R3 is independently selected from: H, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxycarbonyl, phenyl, naphthyl, phenoxy, naphthoxy, C1-C8 haloalkyl, halogen, or R3 connected to R2 to form a 5-7 membered carbon ring or heterocycle.

2. The method for preparing the vicinal diol compound according to claim 1, characterized in that, R1 is selected from: one or more R3-substituted or unsubstituted phenyl groups, one or more R3-substituted or unsubstituted naphthyl groups, one or more R3-substituted or unsubstituted thiophene groups, and one or more R3-substituted or unsubstituted furanyl groups.

3. The method for preparing the vicinal diol compound according to claim 1, characterized in that, Each R3 is independently selected from: H, methyl, ethyl, isobutyl, tert-butyl, propyl, pentyl, hexyl, methoxy, phenoxy, methylthio, methoxyformyl, phenyl, trifluoromethyl, fluorine, chlorine, bromine; or R3 is connected to R2 to form a 6-membered carbon ring.

4. The method for preparing the vicinal diol compound according to claim 1, characterized in that, R3 is isopropyl.

5. The method for preparing the vicinal diol compound according to claim 1, wherein R2 is selected from: H, C1-C3 alkyl, one or more R3-substituted or unsubstituted phenyl groups.

6. The method for preparing the vicinal diol compound according to claim 5, characterized in that, R2 is selected from: H, methyl, ethyl, propyl, phenyl, fluorophenyl, chlorophenyl, and methoxy-substituted phenyl.

7. The method for preparing the vicinal diol compound according to claim 1, characterized in that, The compounds of formula (I) are selected from: The vicinal diol compound represented by formula (II) is selected from: 。 8. The method for preparing the vicinal diol compound according to any one of claims 1-7, characterized in that, The power of the illumination is 20W-40W; and / or, The molar ratio of the compound of formula (I) to the reducing agent is 1:1-3; and / or, The reaction temperature is 15℃-40℃.

9. The method for preparing the vicinal diol compound according to claim 8, characterized in that, The reducing agent is selected from at least one of potassium formate, sodium formate, and cesium formate; and / or, The power of the illumination is 25W-35W; and / or, The solvent is selected from at least one of dimethyl sulfoxide, methanol, ethanol, isopropanol, n-propanol, and n-butanol; and / or, the molar ratio of the compound of formula (I) to the reducing agent is 1:1.5-2.5; and / or, The reaction temperature is 20℃-30℃.

10. The method for preparing the vicinal diol compound according to claim 9, characterized in that, The wavelength of the illumination is 363nm-367nm.

11. The method for preparing the vicinal diol compound according to claim 10, characterized in that, The wavelength of the light is 365 nm.

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