An ester of tocopherol and a method for synthesizing and using the same

Abstract

The application provides an ester of tocopherol and a synthesis method and application thereof, and the ester is obtained by reacting any one of the following acids with any one of the following alcohols: ferulic acid, TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid and trans-4-benzyloxycarbonylaminomethylcyclohexane-1-carboxylic acid. The compound is obtained by catalyzing reaction by using a catalyst. The compound has an antioxidant property.

Description

Technical Field

[0001] This invention relates to new materials and new chemical methods, specifically to a novel ester compound and its applications, as well as a method for its catalytic synthesis. Background Technology

[0002] Thioacids have seen tremendous development in the fields of biosynthetic chemistry and pre-biological chemistry. They are often regarded as key precursors in peptide formation or as sulfur donors for constructing biologically significant natural products. Recent research has shown that thioacids can also serve as highly efficient acylation reagents, exhibiting broad reactivity towards a variety of functional groups, including azides, isonitriles, sulfonamides, nitroso derivatives, isocyanates, aziridines, and thiocarbamates, thus providing a series of synthetically attractive methodologies for the construction of amide bonds.

[0003] In the field of organic synthetic chemistry, photo-redox catalysis driven by green visible light is considered a new revival. It provides a completely new research blueprint for the chemistry of active intermediates and related novel chemical transformations, which are often difficult to achieve in traditional synthetic methods.

[0004] Esterification, one of the most fundamental and important reactions in organic chemistry, occupies a central position in the entire chemical industry. This reaction is not only a key step in the synthesis of many fine chemicals such as pharmaceuticals, fragrances, solvents, plasticizers, and polymers, but also an important means of modifying and functionalizing natural products. Ester bonds formed through esterification are ubiquitous in biomolecules (such as lipids, waxes, and peptide modifiers), thus giving this reaction an irreplaceable role in biochemistry and materials science. With the deepening development of green chemistry, efficient, selective, and environmentally friendly esterification methods have become a continuous pursuit in industry. Achieving high-yield esterification reactions under mild conditions has become an important research direction for promoting sustainable chemical production. Summary of the Invention

[0005] This invention presents a mild and highly efficient esterification reaction method. It is particularly effective for reactions between complex acids and complex alcohols.

[0006] This invention provides an application of an iridium catalyst in esterification reactions, wherein the iridium catalyst is a compound with the following structure: .

[0007] In the above applications, the esterification reaction is the esterification reaction between thioacid and alcohol.

[0008] The present invention also provides an esterification reaction, which occurs in the presence of an iridium catalyst; The iridium catalyst is a compound with the following structure: .

[0009] The esterification reaction proposed in this invention involves the acid first undergoing sulfidation to form a thioacid, which then reacts with an alcohol.

[0010] The reaction takes place in esters or haloalkanes.

[0011] The reaction requires the addition of an alkaline agent, preferably an inorganic alkaline agent.

[0012] The reaction was carried out under 380nm light irradiation.

[0013] This invention also provides an ester prepared based on the above-mentioned esterification reaction, wherein the ester is prepared by reacting any one of the following acids: ferulic acid, TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid, and vitamin B7 with any one of the following alcohols: resveratrol, ergosterol, and tocopherol, and its structural formula is shown below: RCOOR'; Where R is selected from , , , ; R' is selected from , , , , .

[0014] When R' is selected , , hour; At least one hydroxyl group can be substituted with an R, that is, forming a polyester compound.

[0015] The aforementioned esters have antioxidant effects and can be used to manufacture cosmetics, skin care products, etc. with antioxidant functions. Attached Figure Description

[0016] Figure 1 The antioxidant performance test results of the products in the examples. Detailed Implementation

[0017] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] The catalyst Cat.IV mentioned in this embodiment is as follows (the amount used is the general catalytic amount):

[0019] Cat. V: Iridium tetrachloride 10025-97-5M=334.02 Beijing Bailingwei Technology Co., Ltd. Cat. VI: Iridium trichloride trihydrate 13569-57-8M=316.58 Shanghai Mairui Biochemical Technology Co., Ltd. Cat. VII: Tripyridine ruthenium chloride hexahydrate 50525-27-4M=623.1 Shanghai Maclean Biochemical Technology Co., Ltd.

[0020] The aryl group mentioned in this embodiment is a group comprising at least one aromatic hydrocarbon moiety, and can be a monocyclic, polycyclic, or fused-ring polycyclic functional group. In some examples, the aryl group is a general aryl group such as phenyl or naphthyl. In other examples, it can also be a biphenyl or terphenyl group linked by a σ bond. In still other examples, it can be a directly or indirectly fused fluorenyl group. In still other examples, it can also be in a form where at least one hydrogen atom on the aforementioned aryl group is replaced by a substituent, which can be selected from hydroxyl, cyano, amino, nitro, halogen, alkyl, alkoxy, heterocyclic alkyl, alkenyl, alkynyl, ester, etc. In still other examples, any one or more carbon atoms on the aryl ring of the aforementioned aryl group are replaced by a carbonyl group.

[0021] A heteroaryl group is one in which any one or more carbon atoms on the aryl ring of the aforementioned aryl group are replaced by O, N, or S.

[0022] The alkyl group is a straight-chain or branched alkyl group with any number of carbon atoms, or a cycloalkyl group. In some examples, the alkyl group may also be in the form where at least one hydrogen atom on the aforementioned alkyl carbon chain / ring is replaced by a substituent, which may be selected from hydroxyl, cyano, amino, nitro, halogen, alkyl, alkoxy, heterocyclic, alkenyl, alkynyl, aryl, heteroaryl, ester, etc. In some other examples, any one or more carbon atoms on the aforementioned alkyl group are replaced by a carboxyl group. In still other examples, the alkyl group may also be in the form where at least one carbon atom on the aforementioned alkyl carbon chain is replaced by O, N, or S.

[0023] The alkenyl group can be a straight-chain or branched alkenyl group with any number of carbon atoms, or a cycloalkenyl group. In some experimental examples, the alkenyl group can also be in the form where at least one hydrogen atom on the aforementioned alkenyl carbon chain is replaced by a substituent, which can be selected from hydroxyl, cyano, amino, nitro, halogen, alkyl, alkoxy, heterocyclic, alkenyl, alkynyl, aryl, heteroaryl, ester, etc. In some other experimental examples, any one or more carbon atoms on the aforementioned alkenyl group are replaced by a carbonyl group. In still other experimental examples, the alkyl group can also be in the form where at least one carbon atom on the aforementioned alkyl carbon chain is replaced by O, N, or S.

[0024] In this embodiment, an iridium-catalyzed esterification reaction is presented. Based on the findings of this study, esterification reactions between almost all acids R-COOH and alcohols R'OH can be achieved under the catalysis of a specific iridium catalyst. R and R' can be selected from any group such as aryl, heteroaryl, alkyl, or alkenyl. The source of -OH can also be polyhydroxyenol acids such as ascorbic acid.

[0025] The esterification reaction proposed in this invention involves the acid first undergoing sulfidation to form a thioacid, which then reacts with the alcohol. The reaction is preferably carried out in an ester (a type of organic compound with an ester group (-COO-) as its core functional group, represented by the general formula R-COO-R', where R and R' are hydrocarbon groups, which may be the same or different, such as methyl, ethyl, butyl, etc.) or a haloalkane (a type of organic compound formed by replacing one or more hydrogen atoms in a hydrocarbon molecule with halogen atoms, such as fluorine, chlorine, bromine, iodine, represented by the general formula RX, where R is a hydrocarbon group, such as methyl, ethyl, phenyl, etc.; X is a halogen atom, usually Cl or Br). The reaction requires the addition of an alkaline agent, preferably an alkaline inorganic substance, such as hydroxides, carbonates, bicarbonates, sulfites, etc.

[0026] In some preferred experimental cases, R is selected from , , , ; R' is selected from , , , , .

[0027] When R' is selected , , hour; At least one hydroxyl group is also substituted with an R, i.e., forming a polyester compound.

[0028] For reactions between monobasic acids and monohydric alcohols, the molar ratio of acid to alcohol is generally 1:1-1.5.

[0029] For reactions of complex monocarboxylic acids and complex monocarboxylic alcohols, an excess of alcohol is generally used, i.e., the molar ratio of acid to alcohol is generally 1:5-10.

[0030] For the reaction of a monocarboxylic acid with a polyol, when a monoesterification product is desired as the main product, an excess of alcohol is used, such as an acid:alcohol ratio of 1:2-15; when a polyesterification product is desired as the main product, an excess of acid is used, such as an alcohol:acid ratio of 1:5-15. Similarly, for the reaction of a monocarboxylic alcohol with a polycarboxylic acid, when a monoesterification product is desired as the main product, an excess of acid is used, such as an alcohol:acid ratio of 1:2-15; when a polyesterification product is desired as the main product, an excess of alcohol is used, such as an acid:alcohol ratio of 1:5-15.

[0031] The following example illustrates this point.

[0032] Example 1. Preparation of thiocarboxylic acid substrates The reaction equation is as follows:

[0033] RCOOH can be any acid; that is, R can be any group, such as aryl, heteroaryl, alkyl, or alkenyl.

[0034] To further investigate iridium-catalyzed esterification reactions, this embodiment uses several thiocarboxylic acid substrates as examples. It is important to note that this embodiment only uses acids with different values ​​of R as representatives, and does not imply that esterification is impossible with other values ​​of R. On the contrary, the representative acids provided by this invention demonstrate that the method of this invention can achieve esterification reactions of various carboxylic acid derivatives.

[0035] The thioic acid substrates involved in this embodiment are as follows:

[0036] The reactions described in the above equations were carried out according to the method shown in Angew. Chem. Int. Ed. 2020, 59, 12460-12469. Specifically, thiocarboxylic acids were synthesized by reacting an acid compound with Lawson's reagent. Lawson's reagent (1.10 equivalents) was added to a dichloromethane solution (3.50 mL / mmol) of the corresponding carboxylic acid compound (1.00 equivalents), the reaction flask was sealed, and the mixture was microwaved at 100°C for 10 min. The reaction solution was extracted with dichloromethane (10.0 mL / mmol), washed with water (2 × 10.0 mL / mmol), dried over anhydrous magnesium sulfate, filtered under vacuum, and the solvent was removed under reduced pressure to obtain crude thiocarboxylic acids. This crude product was used directly in the next reaction step. Here, it is assumed that the reaction proceeded to completion, and the amounts used in subsequent reactions are based on the amount of carboxylic acid.

[0037] Example 2. Esterification reaction of benzoic acid and phenol The reaction equation is as follows: .

[0038] Example 2.1. Optimal Reaction Conditions Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product, phenyl benzoate, was obtained in 89% yield (98% purity).

[0039] Example 2.2. Catalyst Screening (Cat. II) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.II (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product, phenyl benzoate, was obtained in 71% yield (98% purity).

[0040] Example 2.3. Catalyst Screening (Cat. III) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.III (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated, and TLC analysis showed no product.

[0041] Example 2.4. Catalyst Screening (Cat. IV) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.IV (0.2 equivalence), phenol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated, and TLC analysis showed no product.

[0042] Example 2.5. Catalyst Screening (Cat. V) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.V (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated, and TLC analysis showed no product.

[0043] Example 2.6. Catalyst Screening (Cat. VI) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.VI (0.2 equivalence), phenol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated, and TLC analysis showed no product.

[0044] Example 2.7. Catalyst Screening (Cat. VII) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I, 1.0 equivalence, catalyst Cat. VII (0.2 equivalence), phenol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated, and TLC analysis showed no product.

[0045] Example 2.8. Screening of photocatalytic conditions (visible light) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), phenol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under visible light for 12 hours. After the reaction was complete, the mixture was concentrated, and TLC showed no product.

[0046] Example 2.9. Screening of photocatalytic conditions (blue light) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under blue LED irradiation for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. The product, phenyl benzoate, was obtained in 18% yield (95% purity).

[0047] Example 2.10. Screening of solvent conditions (ethanol) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I, 1.0 equivalence, 0.2 mol / L of catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of ethanol were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under blue LED illumination for 12 hours. After the reaction was complete, the mixture was concentrated, and TLC showed no product.

[0048] Example 2.11. Solvent Condition Screening (DCM) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of dichloromethane were added to a 15 mL sealed tube (equipped with a magnetic stirrer) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under blue LED illumination for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. The product, phenyl benzoate, was obtained in 40% yield (95% purity). Example 2.12. Screening of solvent conditions (THF) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I, 1.0 equivalence, 0.2 mol / L catalyst Cat.I (0.2 mol / L), phenol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of tetrahydrofuran were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under blue LED illumination for 12 hours. After the reaction was complete, the mixture was concentrated, and TLC showed no product.

[0049] Example 2.13. Screening of bases (KOH) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I, 1.0 equivalence, 0.2 mol / L of catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium hydroxide, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product, phenyl benzoate, was obtained in 65% yield (95% purity).

[0050] Example 2.14. Screening of bases (sodium carbonate) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of sodium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product, phenyl benzoate, was obtained in 74% yield (98% purity).

[0051] Example 2.15. Screening of bases (triethylamine) Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of sodium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated, and TLC showed no product.

[0052] Example 3. An esterification reaction The reaction equation is shown below: .

[0053] Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-I (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), n-butanol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. The product, n-butyl benzoate, was obtained in 95% yield (97% purity).

[0054] Example 4. An esterification reaction The reaction equation is shown below: .

[0055] Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-II (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), 1.2 equivalence of phenol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 h. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. The product, phenyl 3-phenylpropionic acid ester, was given in 91% yield (97% purity).

[0056] Example 5. An esterification reaction The reaction equation is shown below: .

[0057] Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-II (1.0 equivalence), 0.2 mol / L catalyst Cat.I (0.2 mol / L), n-butanol (1.2 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated and purified by rapid silica gel column chromatography. The product, n-butyl 3-phenylpropionate, was given in 85% yield (96% purity).

[0058] Example 6. An esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-III (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of resveratrol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography to obtain the product.

[0059] P1 (2E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-3-hydroxy-5-[(1E)-2-(4-hydroxyphenyl)vinyl]phenyl ester yield 33% (purity 96%).

[0060] 1H NMR (400 MHz, DMSO-d6) δ 9.84 (s, 1H), 9.28 (s, 1H), 9.18 (s, 1H), 7.58 (d, J = 16.0 Hz, 1H), 7.46 – 7.38 (m, 2H), 7.19 (d, J = 1.9 Hz, 1H), 7.08 – 6.93 (m, 4H), 6.84 (d, J = 8.4 Hz, 1H), 6.84 – 6.76 (m, 2H), 6.64 (d,J = 16.0 Hz, 1H), 6.61 (q, J = 2.0 Hz, 2H).

[0061] 13 C NMR (100 MHz, DMSO-d6) δ 164.28, 159.11, 157.86, 153.34, 148.45,148.35, 144.89, 139.44, 129.36, 129.06, 128.93, 127.33, 126.49, 123.81,116.02, 115.51, 115.36, 111.98, 111.91, 108.23, 107.06, 56.12.

[0062] M / Z=404.13.

[0063] P2 (2E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-4-[(1E)-2-(3,5-dihydroxyphenyl)vinyl]phenyl ester yield 32% (purity 96%).

[0064] 1 H NMR (400 MHz, DMSO-d6) δ 9.84 (s, 1H), 9.28 (s, 1H), 9.18 (s, 1H), 7.58 (d, J = 16.0 Hz, 1H), 7.46 – 7.38 (m, 2H), 7.19 (d, J = 1.9 Hz, 1H), 7.08 – 6.93 (m, 4H), 6.84 (d, J = 8.4 Hz, 1H), 6.84 – 6.76 (m, 2H), 6.64 (d,J = 16.0 Hz, 1H), 6.61 (q, J = 2.0 Hz, 2H).

[0065] 13C NMR (100 MHz, DMSO-d6) δ 164.28, 159.11, 157.86, 153.34, 148.45,148.35, 144.89, 139.44, 129.36, 129.06, 128.93, 127.33, 126.49, 123.81,116.02, 115.51, 115.36, 111.98, 111.91, 108.23, 107.06, 56.12.

[0066] M / Z=404.13.

[0067] .

[0068] Example 7. An esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-III (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of ergosterol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. Product P3 was obtained in 55% yield (97% purity): (2E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-(1R,3aS,7S,9aR,9bS,11aR)-1-[(2E,4R)-4,5-dimethylhex-2-enyl]-9a,11a-dimethyl-2,3,3a,3b,4,6,7,8,9,9a,9b,10,11,11a-tetradecano-1H-cyclopenta[1,2-i]phenanthrene-7-yl ester.

[0069] 1 H NMR (400 MHz, DMSO- d 6) δ 9.28 (s, 1H), 7.63 – 7.55 (m, 1H), 7.19(d, J = 1.9 Hz, 1H), 7.03 – 6.96 (m, 1H), 6.84 (d, J = 8.4 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 5.46 (m, 1H), 5.44 – 5.33 (m, 1H), 5.34 (t,J = 4.6 Hz,1H), 4.91 (tt, 1H), 2.50 (m, 1H), 2.39 – 2.30 (m, 1H), 2.17 – 1.74 (m, 7H),1.79 – 1.23 (m, 16H), 1.03 (s, 2H), 0.92 (dd, 3H), 0.83 (s, 3H), 0.82 (dd, 6H).

[0070] 13 C NMR (100 MHz, DMSO- d 6) δ 166.63, 148.45, 148.35, 145.00, 139.78,134.71, 129.84, 127.45, 123.64, 122.29, 116.81, 115.51, 111.38, 72.58, 56.12,53.94, 50.28, 48.42, 42.70, 42.53, 38.55, 37.58, 36.64, 36.37, 33.96, 32.78,32.54, 31.96, 29.08, 26.63, 25.31, 21.93, 19.97, 18.90, 17.57, 13.94.

[0071] M / Z=560.93.

[0072] .

[0073] Example 8. An esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-III (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of tocopherol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. The product P4 was obtained with a yield of 43% (purity 97%). It was (2E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-(2R)-2,5,7,8-tetramethyl-2-[(4R,8R)-4,8,12-trimethyltetrazyl]-3,4-dihydro-2H-chromene-6-yl ester.

[0074] 1H NMR (400 MHz, DMSO- d 6) δ 9.28 (s, 1H), 7.62 – 7.54 (m, 1H), 7.19(d, J = 1.9 Hz, 1H), 7.03 – 6.96 (m, 1H), 6.84 (d, J = 8.4 Hz, 1H), 6.59 (d, J = 16.0 Hz, 1H), 2.73 (m, 2H), 2.22 (s, 2H), 2.15 (s, 2H), 2.10 (s, 2H),1.74 – 1.67 (m, 1H), 1.71 – 1.55 (m, 2H), 1.59 – 1.50 (m, 2H), 1.53 – 1.47(m, 1H), 1.50 – 1.42 (m, 1H), 1.46 – 1.36 (m, 3H), 1.39 – 1.18 (m, 18H), 0.85(dd, 9H), 0.79 (d, J = 6.8 Hz, 3H).

[0075] 13 C NMR (100 MHz, DMSO- d 6) δ 163.97, 148.45, 148.35, 148.07, 144.89,144.45, 126.96, 126.49, 125.12, 124.84, 123.81, 122.11, 115.51, 115.12,111.91, 75.21, 56.12, 39.51, 39.04, 37.12, 37.07, 36.72, 36.67, 33.06, 32.57,31.84, 27.82, 24.64, 24.45, 24.05, 22.72, 21.48, 21.29, 19.46, 19.17, 12.48, 12.18, 11.94.

[0076] M / Z=606.43.

[0077] .

[0078] Example 9. An esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-IV (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of resveratrol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and dissolved in 1 mL of glacial acetic acid, followed by the addition of 1 mL of 30% aqueous hydrogen bromide solution, and stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product was obtained with a P5 content of 25% (purity 96%) (1 r 4 r )-4-(aminomethyl)cyclohexane-1-carboxylic acid-3-hydroxy-5-[(1 E 2-(4-hydroxyphenyl)vinyl]phenyl ester.

[0079] 1 H NMR (400 MHz, DMSO- d 6) δ 7.46 – 7.38 (m, 1H), 7.08 – 6.93 (m, 1H), 6.84 – 6.76 (m, 1H), 6.58 (dt, J = 21.4, 2.1 Hz, 1H), 2.71 – 2.41 (m, 1H), 1.94 – 1.82 (m, 1H), 1.68 – 1.42 (m, 3H), 1.28 – 1.16 (m, 1H).

[0080] 13 C NMR (100 MHz, DMSO- d 6) δ 173.16, 159.04, 157.86, 153.02, 139.24,129.36, 129.06, 128.93, 127.33, 116.02, 112.83, 108.23, 107.94, 43.12, 42.15,37.54, 28.77, 27.55.

[0081] M / Z=367.18.

[0082] Product P6 yield 24% (purity 97%) (1 r 4 r )-4-(aminomethyl)cyclohexane-1-carboxylic acid-4-[(1 E2-(3,5-dihydroxyphenyl)vinyl]phenyl ester.

[0083] 1 H NMR (400 MHz, DMSO- d 6) δ 8.51 (s, 1H), 7.57 – 7.50 (m, 2H), 7.28 –7.20 (m, 2H), 7.03 (dt, J = 16.4, 0.9 Hz, 1H), 6.83 (d, J = 16.2 Hz, 1H), 6.44 (d, J = 1.9 Hz, 2H), 6.17 (t, J = 2.0 Hz, 1H), 2.71 – 2.41 (m, 2H), 1.94 – 1.82 (m, 2H), 1.68 – 1.42 (m, 7H), 1.28 – 1.16 (m, 2H).

[0084] 13 C NMR (100 MHz, DMSO- d 6) δ 173.79, 159.05, 151.24, 140.18, 130.81,129.06, 128.49, 127.07, 121.29, 106.66, 102.28, 43.12, 42.16, 37.54, 28.77,27.55.

[0085] M / Z=367.18.

[0086]

[0087] Example 10. An example of esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-IV (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of ergosterol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated, dissolved in 1 mL of glacial acetic acid, and then 1 mL of 30% aqueous hydrogen bromide solution was added. The mixture was stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. Product P7 was obtained in 72% yield (98% purity). (1) r 4 S )-4-(aminomethyl)cyclohexane-1-carboxylic acid-(1 R ,3a S 7 S ,9a R ,9b S ,11a R )-1-[(3 E 5 R )-5,6-dimethylhept-3-en-2-yl]-9a,11a-dimethyl-2,3,3a,3b,4,6,7,8,9,9a,9b,10,11,11a-tetradecano-1 H -Cyclopentazo[1,2- i ]Phenylenol-7-yl ester.

[0088] 1 H NMR (400 MHz, DMSO- d 6) δ 5.26 – 5.06 (m, 1H), 2.71 – 2.44 (m, 1H), 2.44 – 2.24 (m, 1H), 2.04 – 1.16 (m, 11H), 1.03 (s, 1H), 0.94 – 0.87 (m, 2H), 0.85 (d, J = 7.0 Hz, 1H), 0.82 – 0.77 (m, 2H).

[0089] 13 C NMR (100 MHz, DMSO- d6) δ 175.31, 139.82, 135.32, 134.08, 122.24,72.93, 56.73, 54.77, 50.13, 44.08, 43.12, 42.95, 42.18, 39.83, 38.72, 38.09,37.46, 36.64, 36.35, 33.28, 32.70, 31.93, 28.75, 27.80, 27.58, 27.25, 24.64,21.12, 20.30, 19.97, 18.90, 17.61, 13.11.

[0090] M / Z=537.45.

[0091] .

[0092] Example 11. An example of esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-IV (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of tocopherol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and dissolved in 1 mL of glacial acetic acid, followed by the addition of 1 mL of 30% aqueous hydrogen bromide solution, and stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. Product P8 was obtained in 77% yield (96% purity) (1 s 4 R )-4-(aminomethyl)cyclohexane-1-carboxylic acid-(2 R )-2,5,7,8-Tetramethyl-2-[(4 R 8 R )-4,8,12-trimethyltetrazyl]-3,4-dihydro-2 H -Creno-6-yl ester.

[0093] 1 H NMR (400 MHz, DMSO- d6) δ 2.79 – 2.67 (m, 1H), 2.71 – 2.53 (m, 1H), 2.22 (s, 1H), 2.10 (s, 1H), 1.94 – 1.82 (m, 1H), 1.74 – 1.16 (m, 19H), 0.88 –0.76 (m, 6H).

[0094] 13 C NMR (100 MHz, DMSO- d 6) δ 172.94, 148.07, 143.65, 126.96, 125.24,125.14, 122.17, 75.21, 43.12, 41.93, 39.51, 39.04, 37.54, 37.12, 37.07,36.72, 36.67, 33.06, 32.57, 31.84, 28.77, 27.82, 27.55, 24.64, 24.45, 24.05,22.72, 21.48, 21.29, 19.46, 19.17, 12.45, 12.18, 12.03.

[0095] M / Z=569.48.

[0096] .

[0097] Example 12. An example of esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-V (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of resveratrol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. Product P9 was obtained in 40% yield 5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-3-hydroxy-5-[(1 E 2-(4-hydroxyphenyl)vinyl]phenyl ester.

[0098] 1 H NMR (400 MHz, DMSO- d 6) δ 7.46 – 7.38 (m, 2H), 7.08 – 6.93 (m, 2H), 6.84 – 6.76 (m, 1H), 6.64 – 6.57 (m, 1H), 2.71 (q, J = 10.0 Hz, 1H), 1.84(dtd, J = 13.4, 6.7, 4.9 Hz, 1H), 1.66 – 1.45 (m, 3H), 1.45 – 1.34 (m, 1H), 1.28 (s, 1H).

[0099] 13 C NMR (100 MHz, DMSO- d 6) δ 171.70, 159.04, 158.85, 157.86, 152.42,139.25, 129.36, 129.06, 128.93, 127.33, 116.02, 112.95, 108.23, 108.11,70.93, 65.71, 57.30, 44.35, 34.51, 27.23, 26.78, 24.37, 21.88, 21.83.

[0100] M / Z=482.19.

[0101] Product P10 yield 37% (purity 97%) 5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-4-[(1 E 2-(3,5-dihydroxyphenyl)vinyl]phenyl ester.

[0102] 1 H NMR (400 MHz, DMSO- d 6) δ 8.51 (s, 1H), 7.60 – 7.52 (m, 2H), 7.53(d, J = 1.7 Hz, 1H), 7.40 (s, 1H), 7.27 – 7.19 (m, 2H), 7.03 (dt,J = 16.3, 0.8 Hz, 1H), 6.83 (d, J = 16.2 Hz, 1H), 6.44 (d, J = 1.9 Hz, 2H), 6.17 (t, J = 2.0 Hz, 1H), 3.14 (d, J = 9.8 Hz, 0H), 2.71 (q, J = 10.0 Hz, 2H), 2.49 (s,0H), 1.84 (dtd, J = 13.4, 6.7, 4.9 Hz, 1H), 1.66 – 1.50 (m, 3H), 1.46 (s, 2H), 1.44 – 1.34 (m, 2H), 1.28 (s, 2H).

[0103] 13 C NMR (100 MHz, DMSO- d 6) δ 171.51, 159.05, 158.85, 152.02, 140.18,130.73, 129.06, 128.48, 127.07, 121.49, 106.66, 102.28, 70.93, 65.71, 57.30,44.35, 34.51, 27.23, 26.78, 24.41, 21.88, 21.83.

[0104] M / Z=482.19.

[0105] .

[0106] Example 13. An example of esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-V (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of ergosterol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product P11 was obtained in 62% yield (96% purity) 5-[(3a S 4 S ,6a R)-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-(1 R ,3a S 7 S ,9a R ,9b S ,11a R )-1-[(3 E 5 R )-5,6-dimethylhept-3-en-2-yl]-9a,11a-dimethyl-2,3,3a,3b,4,6,7,8,9,9a,9b,10,11,11a-tetradecano-1 H -Cyclopentazo[1,2- i ]Phenylenol-7-yl ester.

[0107] 1 H NMR (400 MHz, DMSO- d 6) δ 5.26 – 5.06 (m, 1H), 2.71 (q, J = 10.0 Hz,1H), 2.49 – 2.29 (m, 1H), 2.33 – 2.23 (m, 1H), 2.04 – 1.60 (m, 4H), 1.59(dddd, J = 11.0, 5.2, 4.5, 2.1 Hz, 2H), 1.58 – 1.47 (m, 1H), 1.50 – 1.20 (m,6H), 1.03 (s, 1H), 0.94 – 0.77 (m, 6H).

[0108] 13 C NMR (100 MHz, DMSO- d6) δ 173.48, 158.85, 139.73, 135.32, 134.08,122.34, 72.64, 70.93, 65.71, 57.30, 56.73, 54.77, 50.13, 44.35, 44.08, 42.95,39.83, 38.72, 37.72, 36.64, 36.34, 34.07, 33.28, 32.70, 31.93, 27.25, 27.23,26.78, 26.77, 24.64, 24.42, 21.88, 21.83, 21.12, 20.30, 19.97, 18.90, 17.61, 13.11.

[0109] M / Z=652.46.

[0110] .

[0111] Example 14. An example of esterification reaction Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-V (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 10 equivalence of tocopherol, 1.0 equivalence of potassium carbonate, and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product P12 was obtained in 84% yield (98% purity) 5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-(2-] R )-2,5,7,8-Tetramethyl-2-[(4 R 8 R )-4,8,12-trimethyltetrazyl]-3,4-dihydro-2 H -Creno-6-yl ester.

[0112] 1 H NMR (400 MHz, DMSO- d 6) δ 2.79 – 2.70 (m, 1H), 2.49 (t, J= 8.1 Hz,1H), 2.22 (s, 1H), 2.15 (s, 1H), 2.10 (s, 1H), 1.74 – 1.18 (m, 16H), 0.88 –0.76 (m, 5H). 13 C NMR (100 MHz, DMSO- d 6) δ 171.49, 158.85, 148.07, 142.93, 126.87,125.57, 124.98, 122.17, 75.21, 70.93, 65.71, 57.30, 44.35, 39.51, 39.04,37.12, 37.07, 36.72, 36.67, 34.38, 33.06, 32.57, 31.84, 27.82, 27.23, 26.78,24.64, 24.45, 24.37, 24.05, 22.72, 21.88, 21.83, 21.48, 21.29, 19.46, 19.17, 12.44, 12.18, 12.04.

[0113] M / Z=684.49.

[0114] .

[0115] Example 15. An example of esterification reaction Under an argon atmosphere, 0.6 mmol of thiocarboxylic acid int-III (1.0 equivalence), 0.2 mol of catalyst Cat.I, 0.2 mol of resveratrol (0.2 equivalence), 1.0 equivalence of potassium carbonate, and 5 mL of anhydrous ethyl acetate were added to a 50 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. P13 was obtained in 31% yield (98% purity) (2) E )-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-5-{[(2 E )-3-(4-hydroxy-3-methoxyphenyl)-1-oxopropyl-2-enyl]oxy}-3-[(1 E 2-(4-hydroxyphenyl)vinyl]phenyl ester.

[0116] 1 H NMR (400 MHz, DMSO-d 6) δ 9.28 (s, 1H), 7.58 (d, J = 16.0 Hz, 1H),7.46 – 7.38 (m, 1H), 7.19 (d, J = 1.9 Hz, 2H), 7.03 (s, 1H), 7.02 – 6.96 (m,1H), 6.92 (t, J = 1.9 Hz, 1H), 6.88 – 6.76 (m, 2H), 6.64 (d, J = 16.0 Hz, 1H).

[0117] 13 C NMR (100 MHz, DMSO- d 6) δ 164.28, 157.86, 152.78, 148.45, 148.35,144.89, 138.57, 130.33, 129.84, 128.93, 127.99, 126.49, 123.81, 116.02,115.51, 115.36, 114.36, 113.25, 111.91, 56.12.

[0118] M / Z=580.17.

[0119] P14 Yield 28% (purity 96%) (2 E )-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-4-[(1 E )-2-(5-{[(2 E 3-(4-hydroxy-3-methoxyphenyl)-1-oxo-methylene-2-enyl]oxy-3-hydroxyphenyl)vinyl]phenyl ester.

[0120] 1 H NMR (400 MHz, DMSO- d 6) δ 9.28 (s, 1H), 7.58 (d, J = 16.0 Hz, 1H),7.57 – 7.50 (m, 1H), 7.30 – 7.22 (m, 1H), 7.19 (d, J = 2.1 Hz, 1H), 7.08 –6.93 (m, 3H), 6.84 (d, J = 8.3 Hz, 1H), 6.64 (dd, J= 16.0, 4.5 Hz, 1H), 6.61(q, J = 2.0 Hz, 1H).

[0121] 13 C NMR (100 MHz, DMSO- d 6) δ 165.30, 164.28, 159.11, 153.34, 151.59,148.45, 148.35, 144.89, 139.44, 130.81, 130.32, 128.70, 127.33, 126.49,123.81, 120.93, 115.51, 115.42, 115.36, 111.98, 111.91, 108.23, 107.06,56.12.

[0122] M / Z=580.17.

[0123] P15 Yield 14% (purity 96%) (2) E )-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid-4-[(1 E )-2-(3,5-double{[(2 E 3-(4-hydroxy-3-methoxyphenyl)-1-oxopropyl-2-enyl]oxyphenyl)vinyl]phenyl ester.

[0124] 1 H NMR (400 MHz, DMSO- d 6) δ 9.28 (s, 1H), 7.62 – 7.50 (m, 2H), 7.30 –7.22 (m, 1H), 7.19 (d, J = 1.9 Hz, 2H), 7.06 – 6.96 (m, 2H), 6.84 (d, J = 8.3Hz, 1H), 6.64 (dd, J = 16.0, 4.5 Hz, 1H).

[0125] 13 C NMR (100 MHz, DMSO- d6) δ 165.30, 164.28, 152.78, 151.59, 148.45,148.35, 144.89, 138.57, 130.81, 128.70, 128.67, 127.99, 126.49, 123.81,120.93, 115.51, 115.42, 115.36, 114.36, 113.25, 111.91, 56.12.

[0126] M / Z=756.22.

[0127] .

[0128] Example 16. An example of esterification reaction Under an argon atmosphere, thiocarboxylic acid int-IV (0.6 mmol, 1.0 equivalence), catalyst Cat.I (0.2 mol), resveratrol (0.2 equivalence), potassium carbonate (1.0 equivalence), and 5 mL of anhydrous ethyl acetate were added to a 50 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated, dissolved in 1 mL of glacial acetic acid, and then 1 mL of 30% aqueous hydrogen bromide solution was added. The mixture was stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product P16 was obtained in 27% yield (98% purity) trans-4-(aminomethyl)cyclohexane-1-carboxylic acid-3-[(1 E )-2-(4-hydroxyphenyl)vinyl]-5-({[trans-4-(aminomethyl)cyclohexyl]carbonyl}oxy)phenyl ester.

[0129] 1 H NMR (400 MHz, DMSO- d 6) δ 7.46 – 7.38 (m, 1H), 7.14 (d, J = 1.9 Hz,1H), 7.03 (s, 1H), 6.89 (t, J = 1.9 Hz, 0H), 6.84 – 6.76 (m, 1H), 2.71 – 2.41(m, 2H), 1.94 – 1.82 (m, 2H), 1.68 – 1.42 (m, 7H), 1.28 – 1.16 (m, 2H).

[0130] 13C NMR (100 MHz, DMSO- d 6) δ 173.15, 157.86, 152.23, 138.32, 130.33,129.84, 128.93, 127.99, 116.02, 115.79, 114.13, 43.12, 42.15, 37.54, 28.77,27.55.

[0131] M / Z=506.28.

[0132] P17 Yield 26% (purity 97%) trans-4-(aminomethyl)cyclohexane-1-carboxylic acid-4-[(1 E )-2-[3-hydroxy-5-({[trans-4-(aminomethyl)cyclohexyl]carbonyl}oxy)phenyl]vinyl]phenyl ester.

[0133] 1 H NMR (400 MHz, DMSO- d 6) δ 7.57 – 7.50 (m, 1H), 7.28 – 7.20 (m, 1H), 7.08 – 6.93 (m, 1H), 6.58 (dt, J = 21.4, 2.1 Hz, 1H), 2.71 – 2.41 (m, 2H), 1.94 – 1.82 (m, 2H), 1.68 – 1.42 (m, 7H), 1.28 – 1.16 (m, 2H). 13 C NMR (100 MHz, DMSO- d 6) δ 173.79, 173.16, 159.04, 153.02, 151.24,139.24, 130.81, 130.32, 128.49, 127.33, 121.29, 112.83, 108.23, 107.94,43.12, 42.16, 37.54, 28.77, 27.55.

[0134] M / Z=506.28.

[0135] P18 Yield 11% (purity 96%) trans-4-(aminomethyl)cyclohexane-1-carboxylic acid-4-[(1 E )-2-[3,5-bis({[trans-4-(aminomethyl)cyclohexyl]carbonyl}oxy)phenyl]vinyl]phenyl ester.

[0136] 1H NMR (400 MHz, DMSO- d 6) δ 7.57 – 7.50 (m, 1H), 7.28 – 7.20 (m, 1H),7.14 (d, J = 1.9 Hz, 1H), 7.03 (s, 1H), 6.89 (t, J = 1.9 Hz, 0H), 2.71 – 2.41(m, 4H), 1.94 – 1.82 (m, 3H), 1.68 – 1.42 (m, 11H), 1.28 – 1.16 (m, 3H).

[0137] 13 C NMR (100 MHz, DMSO- d 6) δ 173.79, 173.15, 152.23, 151.24, 138.32,130.81, 128.67, 128.49, 127.99, 121.29, 115.79, 114.13, 43.12, 42.16, 37.54,28.77, 27.55.

[0138] M / Z=645.38.

[0139] .

[0140] Example 17. An example of esterification reaction Under an argon atmosphere, 0.6 mmol of thiocarboxylic acid int-V (1.0 equivalence), 0.2 mol of catalyst Cat.I (0.2 mol), 0.2 equivalence of resveratrol, 1.0 equivalence of potassium carbonate, and 5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred under 380 nm LED light for 12 hours. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. The product P19 was obtained in 33% yield (98% purity) 5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-5-({5-[(3a] S 4 S ,6a R)-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]-1-oxylidenepentyl)-3-[(1 E 2-(4-hydroxyphenyl)vinyl]phenyl ester.

[0141] 1 H NMR (400 MHz, DMSO- d 6) δ 9.84 (s, 1H), 7.58 (s, 1H), 7.46 – 7.39 (m, 2H), 7.40 (s, 2H), 7.21 (d, J = 1.8 Hz, 2H), 7.03 (s, 2H), 6.89 (t, J =2.0 Hz, 1H), 6.84 – 6.76 (m, 2H), 3.14 (d, J = 9.8 Hz, 1H), 2.71 (q, J = 10.0Hz, 4H), 2.49 (s, 1H), 1.84 (dtd, J = 13.4, 6.7, 4.9 Hz, 2H), 1.66 – 1.51 (m,6H), 1.54 – 1.48 (m, 0H), 1.46 (s, 4H), 1.45 – 1.34 (m, 4H), 1.28 (s, 4H).

[0142] 13 C NMR (100 MHz, DMSO- d 6) δ 171.70, 158.85, 157.86, 151.76, 138.35,130.33, 129.84, 128.93, 127.99, 116.02, 115.31, 114.19, 70.93, 65.71, 57.30,44.35, 34.51, 27.23, 26.78, 24.37, 21.88, 21.83.

[0143] M / Z=736.30.

[0144] P20 yield 28% (purity 97%) 5-[(3a S 4 S ,6a R)-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-4-[(1 E )-2-[5-({5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]-1-oxo-methylene-pentyl]oxy)-3-hydroxyphenyl]vinyl]phenyl ester.

[0145] 1 H NMR (400 MHz, DMSO- d 6) δ 7.60 – 7.50 (m, 2H), 7.40 (s, 1H), 7.27 –7.19 (m, 1H), 7.08 – 7.00 (m, 1H), 6.97 (d, J = 16.2 Hz, 0H), 6.64 – 6.57 (m,1H), 3.14 (d, J = 9.8 Hz, 0H), 2.71 (q, J = 10.0 Hz, 2H), 2.47 (td, J = 8.1, 1.0 Hz, 2H), 1.84 (dtd, J = 13.5, 6.7, 4.9 Hz, 1H), 1.66 – 1.45 (m, 6H), 1.45 – 1.33 (m, 2H), 1.28 (s, 2H).

[0146] 13 C NMR (100 MHz, DMSO- d 6) δ 171.70, 171.51, 159.04, 158.85, 152.42,152.02, 139.25, 130.81, 130.32, 128.48, 127.33, 121.49, 112.95, 108.23,108.11, 70.93, 65.71, 57.30, 44.35, 34.51, 27.23, 26.78, 24.41, 24.37, 21.88,21.83.

[0147] M / Z=736.30.

[0148] P21 yield 9% (purity 96%) 5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]valerate-4-[(1 E )-2-[3,5-double({5-[(3a S 4 S ,6a R )-3a,6a-dimethyl-2-oxo-2,3,3a,4,6,6a-hexahydro-1 H -Thiophene[4,3- d [Imidazol-4-yl]-1-oxopentyl]oxy)phenyl]vinyl]phenyl ester.

[0149] 1 H NMR (400 MHz, DMSO- d 6) δ 7.60 – 7.50 (m, 1H), 7.40 (s, 1H), 7.26 –7.19 (m, 1H), 7.03 (s, 1H), 3.14 (d, J = 9.8 Hz, 0H), 2.71 (q, J = 10.0 Hz,2H), 2.51 – 2.43 (m, 1H), 1.84 (dtd, J = 13.5, 6.7, 4.9 Hz, 1H), 1.66 – 1.58(m, 1H), 1.61 – 1.54 (m, 1H), 1.58 – 1.48 (m, 1H), 1.46 (s, 2H), 1.45 – 1.33(m, 2H), 1.28 (s, 2H).

[0150] 13 C NMR (100 MHz, DMSO- d6) δ 171.70, 171.51, 158.85, 152.02, 151.76,138.35, 130.81, 128.67, 128.48, 127.99, 121.49, 115.31, 114.19, 70.93, 65.71,57.30, 44.35, 34.51, 27.23, 26.78, 24.41, 24.37, 21.88, 21.83.

[0151] M / Z=990.41.

[0152] .

[0153] Example 18 Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-VI (1.0 equivalence), 0.2 mol / L of catalyst Cat.I (0.2 mol / L), ascorbic acid (1.0 equivalence), potassium carbonate (1.0 equivalence), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated and purified by silica gel column chromatography. Product P22 was obtained in 67% yield and with a purity of 93%.

[0154] 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid-(2 R )-2-[(1 S [1,2-Dihydroxyethyl]-4-hydroxy-5-oxo-2,5-dihydrofuran-3-yl ester.

[0155] 1 H NMR (400 MHz, DMSO- d 6) δ 9.36 (s, 1H), 4.97 (d, J = 9.5 Hz, 1H), 4.79 (d, J = 7.0 Hz, 1H), 4.37 (t, J = 7.8 Hz, 1H), 4.04 (dq, J = 9.7, 7.0Hz, 1H), 3.81 (ddd, J = 12.4, 7.7, 6.9 Hz, 1H), 3.67 (ddd, J= 12.4, 7.7, 7.1Hz, 1H), 2.52 (q, J = 7.0 Hz, 1H), 2.21 (hept, J = 6.9 Hz, 1H), 1.79 – 1.47(m, 5H), 1.42 – 1.30 (m, 3H), 1.26 (dd, J = 12.4, 7.0 Hz, 1H), 1.01 – 0.88(m, 24H).

[0156] 13 C NMR (100 MHz, DMSO- d 6) δ 172.56, 169.61, 138.97, 127.80, 77.89,71.16, 63.61, 49.82, 49.40, 46.83, 35.20, 33.01, 32.27, 31.76, 30.57, 29.41,29.27, 25.73, 20.89, 18.53.

[0157] M / Z=442.39.

[0158] .

[0159] Example 19

[0160] Under an argon atmosphere, 0.2 mmol of thiocarboxylic acid int-VI, 0.2 mol / L (0.2 mol / L) of catalyst Cat.I (0.2 mol / L), ascorbic acid (1.0 mol / L), potassium carbonate (1.0 mol / L), and 1.5 mL of anhydrous ethyl acetate were added to a 15 mL sealed tube (equipped with a magnetic stir bar) that had been dried in an oven. The reaction mixture was degassed by a freeze-evacuation-thawing method and then sealed with a sealing film. The solution was placed at room temperature and stirred for 12 hours under 380 nm LED light. After the reaction was complete, the mixture was concentrated and purified by silica gel rapid column chromatography. Product P23 was obtained in 50% yield and with a purity of 95%.

[0161] 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid-(2 S )-2-[(2 R )-3-{[2-(4,4-dimethylpent-2-yl)-5,7,7-trimethyl-1-oxylidene octyl]oxy}-4-hydroxy-5-oxylidene-2,5-dihydrofuran-2-yl]-2-hydroxyethyl ester.

[0162] 1H NMR (400 MHz, DMSO- d 6) δ 4.48 – 4.26 (m, 1H), 1.77 – 1.55 (m, 1H), 1.55 – 1.39 (m, 1H), 1.43 – 1.31 (m, 1H), 1.01 – 0.88 (m, 9H).

[0163] 13 C NMR (100 MHz, DMSO- d 6) δ 174.57, 172.21, 168.08, 135.36, 128.46,77.80, 71.05, 65.52, 50.51, 50.43, 50.00, 49.83, 44.80, 44.73, 34.38, 34.34,33.00, 32.94, 30.81, 30.78, 28.81, 28.79, 28.78, 28.76, 28.74, 28.72, 28.71,28.68, 26.27, 26.23, 21.33, 21.31, 18.70, 18.64.

[0164] M / Z=708.45.

[0165] Product P24 was obtained with a yield of 31% and a purity of 91%.

[0166] 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid-(2 R )-2-[(1 S )-1-{[2-(4,4-dimethylpent-2-yl)-5,7,7-trimethyl-1-oxylidene octyl]oxy}-2-hydroxyethyl]-4-hydroxy-5-oxylidene-2,5-dihydrofuran-3-yl ester.

[0167] 1 H NMR (400 MHz, DMSO- d 6) δ 9.36 (s, 0H), 3.96 – 3.76 (m, 1H), 2.43(dq, J = 8.3, 7.0 Hz, 1H), 2.20 (dhept, J = 11.4, 6.8 Hz, 1H), 1.77 – 1.29 (m, 7H), 1.01 – 0.94 (m, 13H), 0.97 – 0.88 (m, 7H).

[0168] 13 C NMR (100 MHz, DMSO- d 6) δ 173.83, 172.21, 168.15, 135.80, 128.73,76.77, 73.86, 62.20, 51.10, 50.51, 50.43, 50.00, 44.80, 44.73, 34.38, 34.34,33.00, 32.94, 30.81, 30.78, 28.81, 28.79, 28.78, 28.76, 28.74, 28.72, 28.71,28.68, 26.27, 26.23, 21.33, 21.31, 18.70, 18.64.

[0169] M / Z=708.45.

[0170] .

[0171] Example 20. Method Comparison Experiment Example 20.1. Reaction of ferulic acid with resveratrol by sulfoxide esterification. Ferulic acid (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Resveratrol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0172] Example 20.2. Reaction of ferulic acid with ergosterol by sulfoxide esterification. Ferulic acid (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Ergosterol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0173] Example 20.3. Reaction of ferulic acid with tocopherol by sulfoxide esterification. Ferulic acid (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Tocopherol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0174] Example 20.4. Reaction of TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid with resveratrol by sulfoxide esterification. TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Resveratrol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0175] Example 20.5. The reaction of TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid with ergosterol was carried out by sulfoxide esterification. TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Ergosterol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0176] Example 20.6. Reaction of TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid with tocopherol by sulfoxide esterification. TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Tocopherol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0177] Example 20.7. Reaction of Vitamin B7 with Resveratrol using sulfoxide esterification. Vitamin B7 (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Resveratrol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0178] Example 20.8. Reaction of Vitamin B7 with Ergosterol using sulfoxide esterification. Vitamin B7 (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Ergosterol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0179] Example 20.9. Reaction of Vitamin B7 with Tocopherol using sulfoxide esterification. Vitamin B7 (0.2 mmol) was dissolved in 5 mL of 1,2-dichloroethane. One drop of DMF was added as a catalyst at 0°C, followed by the addition of 0.3 mmol of thionyl chloride. The reaction was gradually brought to room temperature and carried out for 1 hour. The solvent was evaporated at low temperature, and the solution was then dissolved in 5 mL of pyridine. Tocopherol (0.2 mmol) was added, and the reaction was carried out at room temperature for 2 hours. No product was detected by TLC.

[0180] Example 21 In vitro antioxidant capacity test To verify the technical effects of the compounds described in this invention, in vitro antioxidant capacity tests were conducted using compounds P1–P24.

[0181] 1. Experimental objective: To verify the in vitro antioxidant capacity of compounds P1–P24 obtained in this invention.

[0182] 2. Test method: Prepare a 0.1% (m / m) sample solution. Prepare the reaction system in a 96-well plate according to the amount of each reagent added in Table 1. Mix well. Set up 3 replicates and 1 background control well for each concentration.

[0183] Table 1 ABTS Free Radical Scavenging Test Reaction System ABTS working fluid 200 200 0.1% of the sample solution to be tested 0 10 PBS 10 0 After incubating at room temperature for 2-6 minutes, the absorbance OD value was read at 734 nm, and the scavenging rate of the sample against ABTS free radicals was calculated using the following formula.

[0184] Clearance rate (%) = ; In the formula: C - Solvent control well absorbance; T - Absorbance value of the sample well.

[0185] 3. Results of Trolox ABTS free radical scavenging rate test.

[0186] Table 2. ABTS radical scavenging rate of different samples

[0187] Note: When performing statistical analysis using the t-test method, significance compared with the negative control group is indicated by *, P-value < 0.05 is indicated by *, and P-value < 0.01 is indicated by **.

[0188] in conclusion Compounds P1-P24 of this invention significantly improved the ABTS radical scavenging rate at a concentration of 0.1% (m / m), with ABTS radical scavenging rates of 61.2%, 63.5%, 63.5%, 65.1%, 66.8%, 68.0%, 69.4%, 70.6%, 71.93%, 72.3%, 73.8%, 74.5%, 75.2%, 76.0%, 76.8%, 77.5%, 78.13%, 78.65%, 79.0%, 79.27%, 79.7%, 80.0%, and 78.9%, respectively. This indicates that compounds P1-P24 can enhance the ABTS radical scavenging rate and possess antioxidant activity. Compared with antioxidants ferulic acid, tocopherol, and resveratrol, some compounds of this invention exhibited higher ABTS radical scavenging capabilities at the same test concentration.

[0189] The function and effect of this embodiment: This study demonstrates that iridium catalysis enables highly efficient esterification reactions under mild reaction conditions. Notably, this method is applicable not only to the esterification of traditional monofunctional acids and alcohols but also to the esterification of complex polyfunctional acids such as ferulic acid, TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid, and vitamin B7 with complex polyfunctional alcohols such as resveratrol, ergosterol, and tocopherol. Furthermore, these esters exhibit antioxidant properties.

Claims

1. An esterified tocopherol, characterized in that, Its structural formula is shown below: RCOOR'; Where R is selected from , , ; R' is selected from .

2. The esterified compound according to claim 1, characterized in that, The compound has the following structure: ， ， 。 3. The use of the esterified compound as an antioxidant as described in any one of claims 1-2.

4. The use of the esterified compound as described in any one of claims 1-2 in the manufacture of cosmetics and skin care products.

5. The method for synthesizing the esterified compound according to any one of claims 1-2, characterized in that: Acids and alcohols undergo esterification reactions in the presence of an iridium catalyst; The iridium catalyst is a compound with the following structure: ； The acid is selected from ferulic acid, TRANS-4-((((benzyloxy)carbonyl)amino)methyl)cyclohexane-1-carboxylic acid, and trans-4-benzyloxycarbonylaminomethylcyclohexane-1-carboxylic acid; The alcohol is selected from tocopherols; In the esterification reaction, the acid is first sulfidated to form a thioacid, and then reacts with the alcohol. The esterification reaction is carried out in an ester or a haloalkane; The esterification reaction was carried out under 380 nm light irradiation; The esterification reaction requires the addition of an alkaline agent, which is an alkaline inorganic substance.

6. The method for synthesizing the esterified compound as described in claim 5, characterized in that: The esterification reaction is carried out under protective gas conditions.

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