A method for photocatalytic synthesis of thioester compounds

Abstract

The application discloses a method for photocatalytic synthesis of thioester compounds and belongs to the field of organic synthesis. The method comprises the following steps: under the condition of a photocatalyst, primary alcohol, S8 and olefin are subjected to hydrogen transfer and coupling reaction in an inert gas atmosphere and an organic solvent, so that thioester compounds are obtained. The application provides a new method for photocatalytic synthesis of thioester. The application uses primary alcohol, S8 and olefin as starting materials, and realizes rapid construction of thioester compounds through hydrogen transfer and coupling reaction of primary alcohol, S8 and olefin under the condition of photocatalysis. The method has the advantages of mild conditions, high economy, good regioselectivity and wide substrate range; S8 can be used as a sulfur source to participate in the construction of thioester and also can be used as a hydrogen acceptor to promote the dehydrogenation of primary alcohol, thereby avoiding the use of an additional oxidant or hydrogen acceptor, and meanwhile, the use of malodorous and unstable mercaptan can be avoided.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and more specifically to a method for photocatalytic synthesis of thioester compounds. Background Technology

[0002] Ester functional groups are widely found in various natural products, bioactive compounds, pharmaceuticals, polymers, and foods. In synthetic chemistry, they can be used as acyl transfer agents to prepare various carbonyl compounds and natural chemical linkages. Thioesters, in particular, play a crucial role in various biological processes, as demonstrated by acetyl-CoA in the metabolism of proteins, lipids, and carbohydrates. Therefore, the synthesis of thioesters has attracted considerable interest from chemists in organic and biosynthetic chemistry. Conventional methods for synthesizing thioesters typically involve the acylation of thiols with acyling agents (mainly derivatives of carboxylic acids) in the presence of activating reagents or catalysts, which generates significant waste and byproducts. Another method involves the oxidative coupling of aldehydes with thiols, usually requiring stoichiometric amounts of oxidant. However, these methods suffer from drawbacks such as the need for excess oxidant and high reaction temperatures. Furthermore, thiols, as sulfur sources, are odorous, unstable, and exhibit a strong affinity for transition metal catalysts, making them less than ideal sulfur sources. On the other hand, alcohols are more stable than aldehydes, widely found in natural products and commercial chemicals, and are ideal starting materials for constructing complex molecules in organic synthesis. In the dehydrogenation coupling reaction of alcohols, alcohols are often used as acyl sources to synthesize a series of carbonyl compounds without the need for an additional oxygen source. Introducing specific molecular fragments can transform alcohols into higher-value products in one step, providing new ideas for fields such as drug synthesis. However, there are only a few reports on the use of primary alcohols as carbonyl precursors to synthesize thioesters via oxidative coupling.

[0003] Therefore, developing a mild and practical technology to synthesize thioester compounds using green and stable sulfur sources and alcohols is of great significance and promise. Summary of the Invention

[0004] To address the shortcomings of the existing technology, one of the objectives of this invention is to provide a method for photocatalytic synthesis of thioester compounds, which utilizes mild photocatalysis to achieve hydrogen transfer coupling of primary alcohols to synthesize thioester compounds.

[0005] The above-mentioned objective of this invention is achieved through the following technical solution:

[0006] A method for photocatalytic synthesis of thioester compounds includes the following steps:

[0007] In an inert gas atmosphere and an organic solvent, the compound shown in formula (I), the element shown in formula (II), and the compound shown in formula (III) undergo hydrogen transfer and coupling reactions under the condition of a photocatalyst to obtain the thioester compound shown in formula (IV).

[0008]

[0009] R 1 Selected from one or more of alkyl, aryl, and heteroaryl groups; R 2 R 3 R 4 Each group is independently selected from one or more of hydrogen, alkyl, aryl, ester, cyclic ketone, amide, and heterocyclic groups.

[0010] This invention uses primary alcohols, S8, and olefins as starting materials to achieve the rapid construction of thioester compounds through hydrogen transfer coupling reactions of primary alcohols, S8, and olefins under photocatalytic conditions, providing a novel method for the photocatalytic synthesis of thioesters. The method of this invention has advantages such as mild conditions, high procedural economy, good regioselectivity, and a broad substrate range. S8 can act as both a sulfur source in the construction of thioesters and a hydrogen acceptor to promote the dehydrogenation of primary alcohols, avoiding the use of additional oxidants or hydrogen acceptors, and also avoiding the use of odorous and unstable thiols.

[0011] Preferred, R 1 Selected from C 1-18 Alkyl, C 6-12 One or more of aryl and 5-10 heteroaryl groups; wherein, each of the above R 1 The alkyl, aryl, or heteroaryl groups are optionally replaced by one or more groups selected from halogen, ester, hydroxyl, C 1-6 Alkyl, phenyl, aryloxy, 5-6 membered heteroaryl, C 3-6 Cycloalkyl substituted;

[0012] R 2 R 3 R 4 Selected independently from hydrogen and C 1-24 Alkyl, C 6-12 Aryl, 5-12 heteroaryl, C 3-12 One or more of cycloalkyl, cycloketyl, and 3-12 membered heterocyclic groups; wherein, the above R 2 R 3 R 4 The alkyl, aryl, heteroaryl, cycloalkyl, and heterocyclic groups are optionally separated by one or more C14 groups. 1-6 Alkyl, phenyl, 5-6 membered heteroaryl, C 3-6 Cycloalkyl, alkoxy, aryloxy, arylate, 5-6 membered heterocyclic groups, -C(=O)R 3a -OC(=O)R 3a -C(=O)NR 3b R 3c or -OC(=O)NR 3b R 3cReplaced;

[0013] or R 3 and R 4 Connect them together to form a 3-12 elemental ring;

[0014] or R 2 and R 3 Connect them together to form a 5-12 elemental ring;

[0015] Among them, R 3a R 3b R 3c Selected independently from C 1-12 Alkyl, alkenyl, C 3-12 cycloalkyl, C 6-12 One or more of aryl and 5-12 heteroaryl groups; wherein, the above R 3a R 3b R 3c The alkyl, alkenyl, cycloalkyl, aryl, and heteroaryl groups are optionally bonded by one or more hydroxyl groups, halogens, or C-terminal groups. 1-6 Alkyl, carbonyl biphenyl, heterocyclic, or heteroaryl substituents; or R 3b With R 3c They connect together to form 3-6 membered heterocyclic groups.

[0016] More preferably, R 1 Selected from C 1-18 One or more of alkyl, alkyl-phenyl, alkyl-ester, biphenyl, methyl ester phenyl, phenoxyphenyl, naphthyl, thiophene, and benzothiophene; wherein each of the above R 1 The alkyl or phenyl groups are optionally replaced by one or more elements selected from halogens, hydroxyl groups, and C. 1-6 Alkyl groups are substituted.

[0017] Preferably, the photocatalyst is a tungstate. This catalyst has high catalytic efficiency.

[0018] Preferably, the molar ratio of the photocatalyst to the compound shown in formula (III) is 1:20.

[0019] Preferably, the molar ratio of the compound shown in formula (I) to the compound shown in formula (III) is (1.5 to 5): 1.

[0020] Preferably, the reaction temperature for the hydrogen transfer and coupling reaction is 35–40°C.

[0021] Preferably, the molar ratio of the element represented by formula (II) to the compound represented by formula (III) is 1:2.2.

[0022] Preferably, the molar volume ratio of the compound shown in formula (III) to the organic solvent is (0.25 to 0.50) mol: 1 L.

[0023] Preferably, the organic solvent includes at least one selected from N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, methanol, and dichloromethane. More preferably, the organic solvent is acetonitrile.

[0024] Compared with the prior art, the advantages of the present invention are:

[0025] (1) This invention uses primary alcohols, S8 and olefins as starting materials, and achieves rapid construction of thioester compounds through hydrogen transfer coupling reaction of primary alcohols, S8 and olefins under photocatalytic conditions, providing a new method for photocatalytic synthesis of thioesters.

[0026] (2) In the method of the present invention, S8 can be used as a sulfur source to participate in the construction of thioesters, and can also be used as a hydrogen acceptor to promote the dehydrogenation of primary alcohols, thus avoiding the use of additional oxidants or hydrogen acceptors.

[0027] (3) This invention does not use malodorous and unstable thiols as a sulfur source, and has the advantages of mild conditions, high step economy, good regional selectivity and wide substrate range. Detailed Implementation

[0028] The technical solution of the present invention will be clearly and completely described below. 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.

[0029] This invention provides a method for photocatalytic synthesis of thioester compounds, comprising the following steps:

[0030] In an inert gas atmosphere and an organic solvent, the compound shown in formula (I), the element shown in formula (II), and the compound shown in formula (III) undergo hydrogen transfer and coupling reactions under the condition of a photocatalyst to obtain the thioester compound shown in formula (IV).

[0031]

[0032] R 1 Selected from one or more of alkyl, aryl, and heteroaryl groups; R 2 R 3 R 4 Each group is independently selected from one or more of hydrogen, alkyl, aryl, ester, cyclic ketone, amide, and heterocyclic groups.

[0033] In some embodiments, the compound represented by formula (I) may be selected from any of the following structures:

[0034]

[0035]

[0036] The compound represented by formula (II) can be selected from any of the following structures:

[0037]

[0038] The compound represented by formula (IV) can be selected from any of the following structures:

[0039]

[0040]

[0041]

[0042] In this invention, the photocatalyst is tetrabutylammonium decatungstate (TBADT), with the following structural formula:

[0043]

[0044] Definitions and general terms

[0045] Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures shall fall within the scope of this application specification.

[0046] Unless otherwise defined, all technical terms in this document have the same meanings as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. Unless otherwise stated, all patents, patent applications, and publications cited in this document are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this document, the definitions in this chapter shall prevail.

[0047] In the context of this invention, all figures disclosed herein are approximate values. The value of each figure may vary by 1%, 2%, 5%, 7%, 8%, or 10%, etc.

[0048] All reaction steps described in this invention proceed to post-processing after reaching a certain stage, such as when the raw material consumption is approximately greater than 70%, 80%, 90%, or 95%, or after detection that the raw materials have been completely consumed. This post-processing includes cooling, collection, extraction, filtration, separation, purification, or combinations thereof. The degree of reaction can be detected using conventional methods such as thin-layer chromatography (TLC), high-performance liquid chromatography (HPLC), and gas chromatography (GC). Conventional methods can be used to post-process the reaction solution. For example, the crude product can be collected by vacuum evaporation or conventional distillation of the reaction solvent and directly added to the next reaction step; or the crude product can be obtained by direct filtration and directly added to the next reaction step; or the supernatant can be poured off after settling to obtain the crude product, which can then be directly added to the next reaction step; or appropriate organic solvents or combinations thereof can be selected for extraction, distillation, crystallization, column chromatography, rinsing, slurrying, and other purification steps.

[0049] In each step of the reaction process described in this invention, the reactants or other reagents can be added to the reaction system dropwise. Each dropwise addition process and each reaction step is carried out under specific temperature conditions; any temperature suitable for use in each dropwise addition process or each reaction process is included in this invention.

[0050] Depending on the choice of raw materials and methods, the compounds of the present invention may exist as one or a mixture of possible isomers, for example as purely optical isomers, or as mixtures of isomers, such as racemic and diastereomeric mixtures, depending on the number of asymmetric carbon atoms. When describing optically active compounds, the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule with respect to the chiral center (or multiple chiral centers) in the molecule. The prefixes D and L or (+) and (–) are symbols used to specify the plane-polarized rotation of light induced by the compound, where (–) or L indicates that the compound is levorotatory. Compounds with the prefix (+) or D are dextrorotatory. For a given chemical structure, these stereoisomers are identical except that they are mirror images of each other. Specific stereoisomers may also be called enantiomers, and mixtures of said isomers are generally referred to as mixtures of enantiomers. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or method. Many geometric isomers of alkenes, C=N double bonds, etc., can also exist in the compounds described herein, and all such stable isomers are considered in this invention. When the compounds described herein contain an alkene double bond, unless otherwise stated, such double bond includes E and Z geometric isomers. If the compound contains a disubstituted cycloalkyl group, the substituent of the cycloalkyl group may be in cis or trans (cis- or trans-) configuration.

[0051] When the bonds of the chiral carbon in the formulas of this invention are depicted as straight lines, it should be understood that both the (R) and (S) configurations of the chiral carbon and the resulting enantiomerically pure compounds and mixtures thereof are included within the scope of the general formula. The illustration of racemic or enantiomerically pure compounds in this document is derived from Maehr, J. Chem. Ed. 1985, 62:114-120. Unless otherwise stated, wedge-shaped and dashed bonds denote the absolute configuration of a stereocenter.

[0052] The compounds of this invention may contain atomic isotopes in non-natural proportions on one or more atoms constituting the compound. For example, the compounds may be labeled with radioactive isotopes, such as deuterium. 2 H), tritium ( 3 H), Iodine-125 125 I) or C-14 14 C). All isotopic variations of the compounds of the present invention, regardless of radioactivity, are included within the scope of the present invention.

[0053] The term "alkyl" should be understood as a straight-chain or branched saturated monovalent, divalent, or trivalent hydrocarbon group consisting of a carbon atom. The term "C1-C" is used to indicate... 24 "Alkyl" should be understood to mean a straight-chain or branched saturated monovalent or polyvalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10... or 24 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, etc., or their isomers. In particular, the group has 1, 2, 3, 4, 5, or 6 carbon atoms ("C1-C6 alkyl"), such as methyl, ethyl, propyl, butyl, or isopropyl; more particularly, the group has 1, 2, or 3 carbon atoms ("C1-C3 alkyl"), such as methyl, ethyl, n-propyl, or isopropyl. Polyvalent hydrocarbon groups include methylene, etc.

[0054] The term "C3-C" 12 "Cycloalkyl" should be understood as referring to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 12 carbon atoms, including fused or bridged polycyclic systems. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or bicyclic hydrocarbons such as decahydronaphthalene ring.

[0055] The term "3-12 membered heterocyclic group" should be understood to mean a saturated, unsaturated, or partially saturated monocyclic, bicyclic, or tricyclic ring having 3 to 12 atoms, wherein 1, 2, 3, 4, or 5 ring atoms are selected from N, O, and S, and unless otherwise stated, they may be linked by carbon or nitrogen, wherein the -CH2- group is optionally replaced by -C(O)-; and wherein, unless otherwise stated to the contrary, the ring nitrogen atom or ring sulfur atom is optionally oxidized to form an N-oxide or S-oxide, or the ring nitrogen atom is optionally quaternized; wherein the -NH in the ring is optionally replaced by an acetyl, formyl, methyl, or methanesulfonyl group; and the ring is optionally replaced by one or more halogens. It should be understood that when the total number of S and O atoms in the heterocyclic group exceeds 1, these heteroatoms are not adjacent to each other. If the heterocyclic group is bicyclic or tricyclic, at least one ring may optionally be a heteroaromatic ring or an aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is monocyclic, it is necessarily not aromatic. Examples of heterocyclic groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinyl, and N-formylpiperazinyl.

[0056] The term "C6-C" 12 "Aryl" should be understood as a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 12 carbon atoms that is monovalent and aromatic or partially aromatic, especially a ring with 6 carbon atoms ("C6 aryl"), such as phenyl; or biphenyl, or a ring with 9 carbon atoms ("C9 aryl"), such as indenyl or indenyl, or a ring with 10 carbon atoms ("C9 aryl"). 10 Aryl), such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl. When the C6-C... 10 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0057] The term "5-12-membered heteroaryl" should be understood as a monovalent monocyclic, bicyclic, or tricyclic aromatic ring group having 5 to 12 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, for example, "5-11-membered heteroaryl". The term "5-12-membered heteroaryl" should also be understood as a monovalent monocyclic, bicyclic, or tricyclic aromatic ring group having 5, 6, 7, 8, 9, 10, 11, or 12 ring atoms—particularly 5, 6, 9, or 10 carbon atoms—and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and, in each case, may be benzo-fused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, etc.

[0058] Throughout this specification, unless otherwise specified, the terminology used herein should be understood as having the meaning commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the event of any conflict, this specification shall prevail.

[0059] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be obtained by purchasing them from the market or by existing methods.

[0060] The following will describe in detail a method for synthesizing thioester compounds from primary alcohols, S8 and olefins by photocatalysis, in conjunction with examples, comparative examples and experimental data.

[0061] Example 1:

[0062]

[0063] Under argon protection, tetrabutylammonium decatungstate (41.5 mg, 0.0125 mmol), S8 (28.9 mg, 0.1125 mmol), phenylpropanol (119.8 mg, 0.875 mmol), 3-methyl-3-buten-1-ylbenzoate (47.5 mg, 0.25 mmol), and acetonitrile (0.5 mL) were added sequentially to a test tube containing a magnetic stir bar. The mixture was placed between two 1W near-UV LEDs (380-390 nm wavelength) and stirred at room temperature for 4 hours. The distance between the LEDs and the quartz reaction vessel was 0.5 cm. After the reaction, the solvent was removed by vacuum distillation. The concentrated solution was purified by column chromatography (petroleum ether / ethyl acetate: 10 / 1) to obtain a colorless oily liquid in 84% yield. 1 H NMR(600MHz,Chloroform-d)δ8.06–8.04(m,2H),7.58–7.55(m,1H),7.46–7.43(m,2H),7.30–7.27(m,2H),7.21–7.18(m,3 H),4.41–4.33(m,2H),3.00–2.97(m,3H),2.91–2.87(m,3H),1.93–1.85(m,2H),1.65–1.60(m,1H),1.03(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ198.3,166.5,140.0,132.9,130.3,129.5,128.5,128.3,128.3,126.3,62.9,45.5,35.5,34.4,31.5,30.7 19.0

[0064] Example 2:

[0065]

[0066] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 1-hexanol (89.4 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 88%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.01(m,2H),7.55–7.52(m,1H),7.43–7.41(m,2H),4.40–4.32(m,2H),2.98–2.95(m,1H),2.88–2.8 5(m,1H),2.54(d,J=9.0Hz,2H),1.94–1.87(m,2H),1.67–1.61(m,3H),1.32–1.27(m,4H),1.03(d,J=6.0Hz,3H),0.88(d,J=9.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ199.3,166.5,132.8,130.2,129.5,128.3,62.9,44.1,35.3,34.4,31.0,30.7,25.3,22.2,19.0,13.8.

[0067] Example 3:

[0068]

[0069] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 1-octadecanol (236.7 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 45%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.56–7.53(m,1H),7.43(t,J=6.0Hz,2H),4.41–4.33(m,2H),2.98–2.95(m,1H),2.89–2. 86(m,1H),2.54(t,J=9.0Hz,2H),1.95–1.87(m,2H),1.68–1.61(m,3H),1.31–1.24(m,28H),1.03(d,J=6.0Hz,3H),0.87(t,J=9.0Hz,3H). 13C NMR(151MHz,Chloroform-d)δ199.4,166.5,132.8,130.3,129.5,128.3,63.0,44.2,3 5.4,34.5,31.9,30.7,29.7,29.6(3),29.4,29.3,29.2,28.9,25.7,22.7,19.0,14.1.

[0070] Example 4:

[0071]

[0072] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 3,7-dimethyl-1-octanol (138.5 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 66%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.02(m,2H),7.55–7.52(m,1H),7.43–7.41(m,2H),4. 40–4.33(m,2H),2.99–2.95(m,1H),2.90–2.86(m,1H),2.56–2.52(m,1H),2.37–2.33(m,1 H),2.03–1.98(m,1H),1.94–1.87(m,2H),1.66–1.60(m,1H),1.54–1.47(m,1H),1.31–1.2 2(m,3H),1.17–1.11(m,3H),1.03(d,J=12.0Hz,3H),0.92–0.91(m,3H),0.86–0.84(m,6H). 13 C NMR(151MHz,Chloroform-d)δ198.9,166.5,132.8,130.3,129.5,128.3,62.9,51 .4,38.9,36.8,35.4,35.3,34.4,31.1,30.7,27.8,24.5,22.6,22.5,19.5,19.0.

[0073] Example 5:

[0074]

[0075] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 4,4,4-trifluorobutanol (112.0 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 65%. 1H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.57–7.54(m,1H),7.45–7.42(m,2H),4.42–4.33(m,2H),3.03–3.00(m,1 H),2.93–2.90(m,1H),2.83–2.80(m,2H),2.51–2.43(m,2H),1.96–1.87(m,2H),1.67–1.62(m,1H),1.04(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ196.0,166.5,132.9,130.2,129.5,128.3,126.3,62.8,36.2,35.6,34.4,30.6,29.3,19.0.

[0076] Example 6:

[0077]

[0078] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with methyl 4-hydroxybutyrate (103.3 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 62%. 1 H NMR(600MHz,Chloroform-d)δ8.02–8.01(m,2H),7.55–7.52(m,1H),7.43–7.41(t,J=7.8Hz,2H),4.39–4.31(m,2H),3.66(s,3 H),3.00–2.97(m,1H),2.90–2.87(m,3H),2.64(t,J=9.0Hz,2H),1.93–1.85(m,2H),1.66–1.60(m,1H),1.02(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ197.5,172.3,166.4,132.8,130.2,129.5,128.3,62.9,51.8,38.4,35.4,34.4,30.6,29.0,18.9.

[0079] Example 7:

[0080]

[0081] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with phenylbutanol (131.3 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 68%. 1 H NMR(600MHz,Chloroform-d)δ8.06–8.04(m,2H),7.57–7.54(m,1H),7.45–7. 42(m,2H),7.31–7.28(m,2H),7.22–7.18(m,3H),4.43–4.35(m,2H),3.01–2.9 8(m,1H),2.92–2.88(m,1H),2.66(t,J=9.0Hz,2H),2.59(t,J=6.0Hz,2H),2. 03–1.98(m,2H),1.97–1.89(m,2H),1.68–1.62(m,1H),1.05(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ199.0,166.6,141.2,132.9,130.3,129.6,128.5,128.4,128.3,126.1,63.0,43.4,35.5,34.5,34.4,30.8,27.2,19.1.

[0082] Example 8:

[0083]

[0084] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 4-chlorophenylpropanol (149.3 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 77%. 1 H NMR(600MHz,Chloroform-d)δ8.05–8.03(m,2H),7.57–7.54(m,1H),7.45–7.42(m,2H),7.25–7.22(m,2H),7.11–7.09(m,2H),4.40–4.32(m,2 H),2.99–2.96(m,1H),2.95–2.92(m,2H),2.89–2.86(m,1H),2.86–2.8 3(m,2H),1.93–1.84(m,2H),1.65–1.59(m,1H),1.01(d,J=6.0Hz,3H). 13C NMR (151MHz, Chloroform-d) δ198.0,166.5,138.4,132.9,132.1,130.2,129.7,129.5,128.6,128.3,62.9,45.2,35.5,34.4,30.7,30.6,19.0.

[0085] Example 9:

[0086]

[0087] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 3-(3-trifluoromethylphenyl)propanol (178.5 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 90%. 1 H NMR(600MHz,Chloroform-d)δ8.05–8.03(m,2H),7.57–7.54(m,1H),7.46–7.42(m,4H),7.40–7.36(m,2H),4.41–4.32(m,2H) ,3.03(t,J=6.0Hz,2H),3.01–2.97(m,1H),2.90–2.87(m,3H),1.93–1.84(m,2H),1.65–1.59(m,1H),1.01(d,J=12.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ197.8,166.5,140.9,132.9,131.8,130.7(q,J=31.7Hz),130.2,129.5,1 28.9,128.3,125.0(q,J=4.5Hz),124.9,123.2(q,J=3.0Hz),62.9,45.0,35.5,34.4,31.1,30.6,18.9.

[0088] Example 10:

[0089]

[0090] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with isopentyl glycol (39.1 mg, 0.375 mmol) to obtain a colorless oily liquid thioester product with a yield of 40%. 1H NMR(600MHz,Chloroform-d)δ7.27(t,J=9.0Hz,2H),7.17(d,J=6.0Hz,3H),3.34(s,1H),3.01–2.98(m,1H),2.86–2.83(m,1H) ,2.74(s,2H),2.70–2.65(m,1H),2.63–2.58(m,1H),1.76–1.69(m,2H),1.55–1.48(m,1H),1.27(s,6H),1.01(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ200.1,142.1,128.3,128.2,125.8,70.2,55.3,37.6,35.6,33.2,32.8,29.0,19.1.

[0091] Example 11:

[0092]

[0093] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 2-cyclohexylethanol (112.2 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 59%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.01(m,2H),7.56–7.53(m,1H),7.44–7 .41(m,2H),4.40–4.33(m,2H),2.98–2.95(m,1H),2.88–2.85(m,1H),2.43(d ,J=6.0Hz,2H),1.94–1.87(m,2H),1.86–1.80(m,1H),1.72–1.61(m,6H),1.2 8–1.20(m,2H),1.16–1.11(m,1H),1.03(d,J=6.0Hz,3H),0.99–0.92(m,2H). 13 C NMR (151MHz, Chloroform-d) δ198.7,166.5,132.8,130.3,129.5,128.3,62.9,51.7,35.6,35.4,34.4,32.8,30.7,26.1,25.9,19.0.

[0094] Example 12:

[0095]

[0096] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 2-cyclopentaneethanol (99.9 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 68%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.56–7.53(m,1H),7.44–7. 41(m,2H),4.41–4.33(m,2H),2.98–2.94(m,1H),2.89–2.86(m,1H),2.56(d, J=6.0Hz,2H),2.30–2.22(m,1H),1.94–1.87(m,2H),1.82–1.77(m,2H),1.65 –1.58(m,3H),1.56–1.49(m,2H),1.19–1.12(m,2H),1.03(d,J=12.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.9,166.5,132.8,130.2,129.5,128.3,62.9,50.1,37.2,35.3,34.4,32.2,30.7,24.8,19.0.

[0097] Example 13:

[0098]

[0099] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 3,3-dimethyl-1-butanol (89.4 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 63%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.02(m,2H),7.56–7.53(m,1H),7.44–7.41(m,2H),4.41–4.33(m,2H),2.96–2.9 3(m,1H),2.88–2.84(m,1H),2.44(s,2H),1.94–1.87(m,2H),1.66–1.60(m,1H),1.03(d,J=6.0Hz,3H),1.02(s,9H). 13 C NMR (151MHz, Chloroform-d) δ197.8,166.6,132.9,130.3,129.6,128.4,63.0,56.9,35.7,34.5,31.6,30.8,29.7,19.1.

[0100] Example 14:

[0101]

[0102] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 1-hydroxyethyladamantane (157.6 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 45%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.56–7.53(m,1H),7.44–7.42(m,2H),4.41–4.34(m,2H),2.9 7–2.94(m,1H),2.88–2.84(m,1H),2.32(s,2H),1.94–1.88(m,3H),1.70–1.60(m,15H),1.03(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ197.1,166.5,132.9,130.3,129.5,128.3,63.0,58.0,42.5,36.7,35.8,34.5,33.7,30.7,28.6,19.1.

[0103] Example 15:

[0104]

[0105] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with isobutanol (64.8 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 53%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.02(m,2H),7.56–7.53(m,1H),7.44–7.41(m,2H),4.41–4.33(m,2H),2.96–2.93(m,1 H),2.88–2.84(m,1H),2.78–2.71(m,1H),1.94–1.87(m,2H),1.67–1.61(m,1H),1.19–1.18(m,6H),1.03(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ203.9,166.5,132.8,130.3,129.5,128.3,62.9,43.2,35.1,34.5,30.8,19.4,19.3,19.0.

[0106] Example 16:

[0107]

[0108] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 2-ethylhexanol (114.0 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 68%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.01(m,2H),7.55–7.52(m,1H),7.43–7.41 (m,2H),4.41–4.33(m,2H),3.00–2.94(m,1H),2.91–2.86(m,1H),2.50–2.45(m ,1H),1.95–1.87(m,2H),1.69–1.61(m,3H),1.54–1.47(m,1H),1.46–1.41(m,1 H),1.31–1.24(m,4H),1.04–1.03(m,3H),0.91–0.88(m,3H),0.87–0.85(m,3H). 13 C NMR(151MHz,Chloroform-d)δ203.3,166.5,132.8,130.3,129.5,128.3,62.9 ,56.2,35.1,35.1,34.5,32.3,30.7,29.4,26.0,22.6,19.0,18.9,13.9,11.7.

[0109] Example 17:

[0110]

[0111] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 1-cyclobutanol (75.3 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 63%. 1 H NMR(600MHz,Chloroform-d)δ8.02(d,J=6.0Hz,2H),7.54(t,J=6.0Hz,1H),7.42(t,J=9.0Hz,2H),4.41–4.33(m,2H),3.37–3.32(m,1H), 2.98–2.94(m,1H),2.89–2.86(m,1H),2.34–2.28(m,2H),2.22–2.17(m,2H),1.97–1.84(m,4H),1.66–1.60(m,1H),1.03(d,J=6.0Hz,3H). 13C NMR (151MHz, Chloroform-d) δ201.2,166.5,132.8,130.3,129.5,128.3,62.9,46.8,35.1,34.5,30.8,26.0,25.9,19.0,17.9.

[0112] Example 18:

[0113]

[0114] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 2,2-dimethyl-4-phenylbutyl-1-ol (155.8 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 46%. 1 H NMR(600MHz,Chloroform-d)δ8.03–8.02(m,2H),7.55–7.52(m,1H),7.41(t,J=6.0Hz,2H),7.27–7.25(m,2H),7.18–7.16(m,3H),4.43–4.35(m,2H),3 .00–2.97(m,1H),2.90–2.87(m,1H),2.54–2.51(m,2H),1.96–1.91(m,2H) ,1.90–1.87(m,2H),1.68–1.64(m,1H),1.29(s,6H),1.06(d,J=6.4Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ205.9,166.5,142.1,132.8,130.3,129.5,128.4, 128.3,128.2,125.8,63.0,50.0,43.3,35.2,34.6,31.2,30.8,25.4,25.3,19.1.

[0115] Example 19:

[0116]

[0117] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 2-ethyl-2-phenylethylhexane-1-ol (204.9 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 33%. 1H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.55–7.52(m,1H),7.44–7.40(m,2H),7. 28–7.25(m,2H),7.19–7.16(m,3H),4.43–4.35(m,2H),3.02–2.99(m,1H),2.91–2.87(m,1H ),2.47–2.44(m,2H),1.95–1.89(m,4H),1.77–1.71(m,2H),1.70–1.62(m,4H),1.33–1.29( m,2H),1.21–1.15(m,2H),1.07–1.04(m,3H),0.90(t,J=9.0Hz,3H),0.83(t,J=9.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ205.7,166.5,142.2,132.8,130.3,129.5,128.4,128.3,128.3,128.2,12 5.8,63.0,56.6,37.0,36.9,35.0,34.6,34.1,34.0,30.8,30.3,27.4,27.3,25.7,23.2,19.1,14.0,8.0.

[0118] Example 20:

[0119]

[0120] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with phenylethanol (106.8 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 28%. 1 H NMR(600MHz,Chloroform-d)δ8.02–8.01(m,2H),7.55(t,J=6.0Hz,1H),7.43(t,J=9.0Hz,2H),7.32(t,J=6.0Hz,2H),7.28–7.25(m,3H ),4.42–4.29(m,2H),3.82(s,2H),2.98–2.95(m,1H),2.88–2.84(m,1H),1.93–1.84(m,2H),1.64–1.58(m,1H),1.01(d,J=6.0Hz,3H). 13C NMR (151MHz, Chloroform-d) δ197.1,166.5,133.7,132.9,130.3,129.5,129.5,128.6,128.3,127.3,62.9,50.5,35.8,34.5,30.7,19.0.

[0121] Example 21:

[0122]

[0123] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with p-tert-butylbenzyl alcohol (143.6 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 57%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.03(m,2H),7.93–7.91(m,2H),7.55–7.52(m,1H),7.47–7.45(m,2H),7.42–7.40(t,J=7.8Hz,2H ),4.45–4.37(m,2H),3.18–3.15(m,1H),3.10–3.16(m,1H),2.06–1.96(m,2H),1.72–1.67(m,1H),1.33(s,9H),1.11(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ191.2,166.5,157.1,134.4,132.8,130.2,129.5,128.3,127.1,125.5,63.0,35.5,35.1,34.5,31.0,30.8,19.1.

[0124] Example 22:

[0125]

[0126] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with biphenylmethanol (161.1 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 66%. 1H NMR(600MHz,Chloroform-d)δ8.07–8.05(m,4H),7.68–7.66(m,2H),7.63(d,J=6.0Hz,2H),7.55(t,J=9.0Hz,1H),7.48(t,J=9.0Hz,2H), 7.44–7.39(m,3H),4.48–4.39(m,2H),3.23–3.20(m,1H),3.14–3.10(m,1H),2.10–2.00(m,2H),1.76–1.70(m,1H),1.14(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ191.1,166.5,146.0,139.7,135.7,132.8,130.2, 129.5,128.9,128.3,128.2,127.8,127.2,127.1,63.0,35.6,34.5,30.8,19.2.

[0127] Example 23:

[0128]

[0129] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with methyl 4-(hydroxymethyl)benzoate (145.4 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 53%. 1 H NMR(600MHz,Chloroform-d)δ8.12–8.10(m,2H),8.04–8.01(m,4H),7.56–7.53(m,1H),7.44–7.41(m,2H),4.46–4.37(m,2H),3.95(s,3 H),3.22–3.19(m,1H),3.12–3.19(m,1H),2.09–2.03(m,1H),2.02–1.96(m,1H),1.75–1.69(m,1H),1.61(s,1H),1.12(d,J=12.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ191.2,166.6,166.1,140.3,134.1,132.9,130.2,129.8,129.5,128.3,127.2,62.9,52.5,35.9,34.6,30.8,19.2.

[0130] Example 24:

[0131]

[0132] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with p-chlorobenzyl alcohol (124.8 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 66%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.92–7.90(m,2H),7.56–7.53(m,1H),7.43–7.41(m,4H),4.46– 4.37(m,2H),3.20–3.16(m,1H),3.10–3.17(m,1H),2.07–1.95(m,2H),1.74–1.69(m,1H),1.11(d,J=12.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ190.5,166.5,139.7,135.4,132.9,130.2,129.5,128.8,128.6,128.3,62.9,35.7,34.5,30.8,19.2.

[0133] Example 25:

[0134]

[0135] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 4-(trifluoromethyl)benzyl alcohol (164.0 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 55%. 1 H NMR(600MHz,Chloroform-d)δ8.07(d,J=6.0Hz,2H),8.03(d,J=6.0Hz,2H),7.71(d,J=12.0Hz,2H),7.54(t,J=9.0Hz,1H),7.42(t,J=9.0Hz,2H),4.47– 4.43(m,1H),4.42–4.37(m,1H),3.23–3.20(m,1H),3.13–3.10(m,1H),2.09 –2.03(m,1H),2.02–1.96(m,1H),1.75–1.69(m,1H),1.12(d,J=6.0Hz,3H). 13C NMR(151MHz,Chloroform-d)δ190.8,166.5,139.8,134.6(q,J=33.2Hz),132.9,130.2,129.5, 128.3,127.6,125.7,125.7,125.6,125.6,123.5(q,J=273.3Hz),62.9,35.9,34.6,30.7,19.2. 19 F NMR(565MHz,Chloroform-d)δ-63.09.

[0136] Example 26:

[0137]

[0138] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 3,5-difluorobenzyl alcohol (126.0 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 53%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.56–7.53(m,1H),7.50–7.46(m,2H),7.44–7.41(m,2H),7.03–6.99(m,1H),4.46– 4.37(m,2H),3.21–3.18(m,1H),3.11–3.08(m,1H),2.08–2.02(m,1H),2.00–1.95(m,1H),1.74–1.68(m,1H),1.11(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ189.4(t,J=2.3Hz),166.5,163.7(d,J=12.1Hz),162.0(d,J=12.1Hz),139.83(t,J=9.1Hz) ,132.9,130.2,129.5,128.3,110.4(d,J=6.0Hz),110.2(d,J=6.0Hz),108.5(t,J=25.7Hz),62.8,36.0,34.5,30.7,19.2. 19 F NMR(565MHz,Chloroform-d)δ-107.77.

[0139] Example 27:

[0140]

[0141] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 3-phenoxybenzyl alcohol (175.1 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 49%. 1 H NMR(600MHz,Chloroform-d)δ8.04–8.02(m,2H),7.72–7.71(m,1H),7.59(t,J=6.0 Hz,1H),7.55–7.52(m,1H),7.43–7.38(m,3H),7.37–7.34(m,2H),7.21–7.19(m,1H ),7.14(t,J=6.0Hz,1H),7.02(d,J=6.0Hz,2H),4.44–4.36(m,2H),3.18–3.14(m,1 H),3.08–3.04(m,1H),2.06–1.95(m,2H),1.72–1.67(m,1H),1.10(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ191.1,166.5,157.7,156.4,138.7,132.8,130.2,130.0, 129.9,129.5,128.3,123.9,123.4,121.9,119.2,116.9,62.9,35.7,34.5,30.8,19.1.

[0142] Example 28:

[0143]

[0144] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with o-methylbenzyl alcohol (106.8 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 40%. 1 H NMR(600MHz,Chloroform-d)δ8.04(d,J=6.0Hz,2H),7.78(d,J=12.0Hz,1H),7.54(t,J=9.0Hz,1H),7.42(t,J=9.0Hz,2H),7.38(t,J=9.0Hz,1H),7.24 (t,J=6.0Hz,2H),4.46–4.38(m,2H),3.16–3.13(m,1H),3.07–3.03(m,1H) ,2.46(s,3H),2.07–1.97(m,2H),1.75–1.69(m,1H),1.12(d,J=6.0Hz,3H). 13CNMR(151MHz,Chloroform-d)δ194.1,166.5,137.7,136.6,132.9,131.5,13 1.4,130.3,129.5,128.4,128.3,125.7,63.0,36.2,34.6,30.8,20.5,19.1.

[0145] Example 29:

[0146]

[0147] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 2-naphthalenemethanol (138.4 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 62%. 1 H NMR(600MHz,Chloroform-d)δ8.55(s,1H),8.05(d,J=6.0Hz,2H),8.02–8.00(m,1H ),7.97(d,J=6.0Hz,1H),7.88(t,J=9.0Hz,2H),7.61–7.85(m,1H),7.57–7.52(m,2 H),7.42(t,J=9.0Hz,2H),4.49–4.40(m,2H),3.26–3.23(m,1H),3.17–3.14(m,1H) ,2.112–2.07(m,1H),2.06–2.01(m,1H),1.77–1.72(m,1H),1.15(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ191.6,166.5,135.7,134.3,132.8,132.4,130.2, 129.5,128.6,128.4,128.3,127.7,126.9,123.1,63.0,35.7,34.6,30.8,19.2.

[0148] Example 30:

[0149]

[0150] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 3-thiophene methanol (99.8 mg, 0.875 mmol) to obtain a colorless oily liquid thioester product with a yield of 62%. 1H NMR(600MHz,Chloroform-d)δ8.12–8.11(m,1H),8.04–8.03(m,2H),7.56–7.53(m,2H),7.42(t,J=6.0Hz,2H),7.33–7.32(m,1H),4.4 5–4.41(m,1H),4.40–4.36(m,1H),3.17–3.14(m,1H),3.08–3.05(m,1H),2.06–1.95(m,2H),1.72–1.67(m,1H),1.10(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ185.2,166.5,140.9,132.9,130.4,130.2,129.5,128.3,126.4,126.0,63.0,35.4,34.5,30.8,19.1.

[0151] Example 31:

[0152]

[0153] The experimental procedure was the same as in Example 1, except that phenylpropanol was replaced with 1-benzothiophene-2-methanol (143.5 mg, 0.875 mmol), and the reaction was carried out for 8 hours to obtain a colorless oily liquid thioester product with a yield of 48%. 1 H NMR(600MHz,Chloroform-d)δ8.07(s,1H),8.05–8.03(m,2H),7.89–7.85(m,2H),7.55–7.52(m,1H),7.48–7.45(m,1H),7.44–7.40(m,3H), 4.47–4.38(m,2H),3.24–3.21(m,1H),3.15–3.12(m,1H),2.10–2.05(m,1H),2.03–1.98(m,1H),1.75–1.70(m,1H),1.13(d,J=12.0Hz,3H). 13 CNMR(151MHz,Chloroform-d)δ185.0,166.5,141.8,141.4,138.6,132.9,130.2 ,129.5,128.3,128.1,127.3,125.8,125.1,122.8,62.9,36.0,34.5,30.9,19.1.

[0154] Example 32:

[0155]

[0156] Under argon protection, tetrabutylammonium decatungstate (41.5 mg, 0.0125 mmol), S8 (28.9 mg, 0.1125 mmol), phenylpropanol (119.8 mg, 0.875 mmol), (3-methylbut-3-en-1-yl)benzene (36.5 mg, 0.25 mmol), and acetonitrile (0.5 mL) were added sequentially to a test tube equipped with a magnetic stir bar. The tube was placed between two 1W near-UV LED lamps and stirred at room temperature for 4 hours. After the reaction was completed, the solvent was removed by vacuum distillation, and the concentrated solution was purified by column chromatography (petroleum ether / ethyl acetate: 10 / 1) to obtain a colorless oily liquid in 77% yield. 1 H NMR(600MHz,Chloroform-d)δ7.31(t,J=6.0Hz,4H),7.24–7.20(m,6H),3.03–3.00(m,3H),2.91–2.85(m ,3H),2.73–2.68(m,1H),2.65–2.61(m,1H),1.77–1.71(m,2H),1.56–1.49(m,1H),1.02(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.5,142.3,140.1,128.5,128.3,128.3,126.3,125.7,45.5,37.6,35.5,33.2,33.0,31.5,19.1.

[0157] Example 33:

[0158]

[0159] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with (2-methylenehexyl)benzene (43.5 mg, 0.25 mmol) and acetonitrile (0.5 mL), resulting in a colorless oily liquid with a yield of 70%. 1 H NMR(600MHz,Chloroform-d)δ7.33–7.29(m,4H),7.24–7.21(m,4H),7.16(d,J=6.0Hz,2H),3.03–3.00(m,2 H),2.94–2.89(m,4H),2.61(d,J=6.0Hz,2H),1.94–1.88(m,1H),1.39–1.27(m,6H),0.91(t,J=9.0Hz,3H). 13C NMR (151MHz, Chloroform-d) δ198.4,140.1,140.0,129.2,128.5,128.3,128.2,126.3,126.0,45.6,39.8,39.8,32.6,32.3,31.5,28.8,22.7,14.0.

[0160] Example 34:

[0161]

[0162] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with methylenecyclododecane (45.1 mg, 0.25 mmol) to obtain a colorless oily liquid thioester product with a yield of 87%. 1 H NMR(600MHz,Chloroform-d)δ7.29(t,J=6.0Hz,2H),7.21(t,J=9.0Hz,3H),2. 99(t,J=9.0Hz,2H),2.89–2.86(m,4H),1.68–1.63(m,1H),1.41–1.27(m,22H). 13 C NMR (151MHz, Chloroform-d) δ198.7,140.1,128.5,128.3,126.2,45.5,34.3,34.2,31.5,28.7,24.4,23.8,23.4,23.3,21.7.

[0163] Example 35:

[0164]

[0165] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-ylvalerate (42.5 mg, 0.25 mmol) to obtain a colorless oily liquid thioester product with a yield of 80%. 1 HNMR(600MHz,Chloroform-d)δ7.28(t,J=9.0Hz,2H),7.21–7.18(m,3H),4.13–4.05(m,2H),2.98(t,J=6.0Hz,2H),2.95–2.92(m,1H), 2.87(t,J=6.0Hz,2H),2.84–2.81(m,1H),1.83–1.77(m,1H),1.76–1.70(m,1H),1.50–1.44(m,1H),1.19(s,9H),0.97(d,J=6.0Hz,3H).13 CNMR(151MHz,Chloroform-d)δ198.3,178.5,140.1,128.5,128.3,126.4,62.3,45.6,38.7,35.5,34.4,31.5,30.7,27.2,19.0.

[0166] Example 36:

[0167]

[0168] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-ylcyclohexane carboxylate (49.0 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 75%. 1 H NMR(600MHz,Chloroform-d)δ7.28(t,J=9.0Hz,2H),7.21–7.18(m,3H),4.14–4. 05(m,2H),2.99–2.96(m,2H),2.94–2.91(m,1H),2.88–2.86(m,2H),2.84–2.81(m ,1H),2.31–2.26(m,1H),1.91–1.88(m,2H),1.83–1.78(m,1H),1.77–1.69(m,3H) ,1.65–1.62(m,1H),1.49–1.40(m,3H),1.31–1.20(m,3H),0.96(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.3,176.0,140.0,128.5,128.3,126.3,62.0,45.5,43.2,35.4,34.3,31.4,30.5,29.0,28.9,25.7,25.4,18.9.

[0169] Example 37:

[0170]

[0171] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 2-phenylbutyrate (58.0 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 69%. 1H NMR (600MHz, Chloroform-d) δ7.31–7.26(m,6H),7.25–7.22(m,1H),7.20–7.17(m,3H),4.14–4.04(m,2H),3.43(t,J=6.0Hz,1H),2.96(t,J=9. 0Hz,2H),2.87–2.83(m,3H),2.77–7.72(m,1H),2.13–2.06(m,1H),1.83 –1.76(m,1H),1.70–1.62(m,2H),1.44–1.37(m,1H),0.90–0.86(m,6H). 13 C NMR(151MHz,Chloroform-d)δ198.2,198.2,173.9,140.0,139.1,139.1,128.5,128.3,127.9,127. 1,126.3,62.6,62.5,53.5,45.5,35.3,35.3,34.2,34.2,31.4,30.5,30.4,26.5,26.5,18.8,12.1.

[0172] Example 38:

[0173]

[0174] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 4-(trifluoromethyl)benzoate (64.5 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 83%. 1 HNMR(600MHz,Chloroform-d)δ8.15(d,J=12.0Hz,2H),7.71(d,J=6.0Hz,2H),7.28(t,J=6.0Hz,2H),7.21–7.18(M,3H) ,4.44–4.36(M,2H),3.01–2.97(m,3H),2.89–2.86(m,3H),1.93–1.86(m,2H),1.68–1.61(m,1H),1.03(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ198.3,165.3,140.0,134.4(q,J=33.2Hz),133.5,130.0,1 28.5,128.3,126.3,125.4(q,J=4.5Hz)122.7,63.5,45.5,35.4,34.3,31.4,30.7,19.0.

[0175] Example 39:

[0176]

[0177] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 3-bromobenzoate (67.0 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 89%. 1 H NMR(600MHz,Chloroform-d)δ8.17(s,1H),7.97(d,J=6.0Hz,1H),7.69–7.67(m,1H),7.32(t,J=6.0Hz,1H),7.28(t,J=6.0Hz,2H),7.2 1–7.18(m,3H),4.41–4.33(m,2H),2.99–2.96(m,3H),2.90–2.86(m,3H),1.92–1.84(m,2H),1.65–1.59(m,1H),1.02(d,J=6.0Hz,3H). 13 CNMR(151MHz,Chloroform-d)δ198.3,165.2,140.0,135.8,132.5,132.2,130. 0,128.5,128.3,128.1,126.3,122.4,63.4,45.5,35.4,34.3,31.5,30.6,19.0.

[0178] Example 40:

[0179]

[0180] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 2-naphthylcarboxylate (60.0 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 75%. 1H NMR(600MHz,Chloroform-d)δ8.62(s,1H),8.08–8.06(m,1H),7.97(d,J=6.0Hz,1H),7.89(d,J=12.0Hz,2H),7.61–7.54(m,2H),7.28(t,J=6.0H z,2H),7.21–7.18(m,3H),4.48–4.40(m,2H),3.04–2.97(m,3H),2.94–2 .87(m,3H),1.99–1.91(m,2H),1.71–1.65(m,1H),1.06(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ198.3,166.7,140.0,135.5,132.5,131.0,129.3,128.5,128.3 ,128.2,128.1,127.7,127.5,126.6,126.3,125.2,63.1,45.5,35.5,34.5,31.5,30.7,19.1.

[0181] Example 41:

[0182]

[0183] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-ylthiophene-2-carboxylic acid ester (49.0 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 74%. 1 H NMR(600MHz,Chloroform-d)δ7.80(t,J=6.0Hz,1H),7.54(t,J=6.0Hz,1H),7.29(t,J=9.0Hz,2H),7.19(t,J=12.0Hz,3H),7.10(d,J =6.0Hz,1H),4.38–4.30(m,2H),3.00–2.95(m,3H),2.90–2.86(m,3H),1.92–1.82(m,2H),1.63–1.57(m,1H),1.01(d,J=12.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.2,162.1,140.0,133.8,133.3,132.3,128.4,128.2,127.7,126.2,63.1,45.4,35.3,34.2,31.4,30.6,19.0.

[0184] Example 42:

[0185]

[0186] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 3-methylbut-2-enoate (42.0 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 72%. 1 HNMR(600MHz,Chloroform-d)δ7.28(t,J=6.0Hz,2H),7.21–7.18(m,3H),5.67–5.66(m,1H),4.16–4.08(m,2H),2.99–2.96(m,2H),2.95–2.92(m,1H) ),2.88–2.82(m,3H),2.16(d,J=6.0Hz,3H),1.89(d,J=6.0Hz,3H),1.85– 1.79(m,1H),1.77–1.71(m,1H),1.51–1.46(m,1H),0.96(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.3,166.6,156.6,140.0,128.4,128.3,126.3,116.0,61.4,45.5,35.4,34.4,31.4,30.5,27.3,20.1,18.8.

[0187] Example 43:

[0188]

[0189] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 10H-phenthiazine-10-carboxylic acid ester (77.8 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 62%. 1 HNMR(600MHz,Chloroform-d)δ7.55(d,J=6.0Hz,2H),7.38–7.36(m,2H),7.31–7.28(m,4H),7.23–7.17(m,5H),4.30–4.21(m ,2H),3.01–2.98(m,2H),2.91–2.87(m,3H),2.79–2.76(m,1H),1.77–1.71(m,2H),1.52–1.46(m,1H),0.93(d,J=6.0Hz,3H). 13C NMR(151MHz,Chloroform-d)δ198.2,153.6,140.0,138.2,132.1,128.5,128.3 ,127.4,127.0,126.7,126.3,126.3,64.5,45.5,35.3,34.3,31.4,30.6,18.8.

[0190] Example 44:

[0191]

[0192] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl diphenylcarbamate (70.3 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 70%. 1 HNMR(600MHz,Chloroform-d)δ7.31(t,J=6.0Hz,4H),7.27(t,J=6.0Hz,2H),7.23(d,J=12.0Hz,4H),7.20–7.17(m,5H),4.23–4.15 (m,2H),2.96(t,J=9.0Hz,2H),2.86–2.81(m,3H),2.73–2.69(m,1H),1.70–1.62(m,2H),1.46–1.40(m,1H),0.87(d,J=6.0Hz,3H). 13 CNMR(151MHz,Chloroform-d)δ198.2,154.7,142.5,140.0,128.8,128.5,128.3,126.9,126.3,126.0,64.0,45.5,35.3,34.5,31.5,30.6,18.8.

[0193] Example 45:

[0194]

[0195] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with dodecene (42.0 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 73%.

[0196] Nuclear magnetic resonance data: 1H NMR(600MHz,Chloroform-d)δ7.29(t,J=6.0Hz,2H),7.22–7.19(m,3H),3.00–2.97(m, 2H),2.89–2.85(m,4H),1.58–1.53(m,2H),1.37–1.27(m,18H),0.89(t,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.7,140.1,128.5,128.3,126.3,45.5,31.9,31.5,29.6(3),29.5(2),29.3,29.1,28.9,28.8,22.7,14.1.

[0197] Example 46:

[0198]

[0199] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with allylbenzene (29.5 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 55%. 1 H NMR (600MHz, Chloroform-d) δ7.25(t,J=9.0Hz,4H),7.18–7.13(m,6H),2.97–2.94(m,2H),2.88–2.82(m,4H),2.64(t,J=6.0Hz,2H),1.89–1.84(m,2H). 13 C NMR (151MHz, Chloroform-d) δ198.3,141.0,140.0,128.4,128.3,128.3,128.2,126.2,125.9,45.4,34.7,31.4,31.0,28.2.

[0200] Example 47:

[0201]

[0202] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with but-3-en-1-ylbenzoate (44.0 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 75%. 1H NMR(600MHz,Chloroform-d)δ8.05(d,J=9.0Hz,2H),7.56(t,J=9.0Hz,1H),7.45(t,J=6.0Hz,2H),7.29(t,J=6.0Hz,2H),7. 20(t,J=9.0Hz,3H),4.33(t,J=6.0Hz,2H),3.00–2.95(m,4H),2.88(t,J=9.0Hz,2H),1.85–1.80(m,2H),1.76–1.71(m,2H). 13 C NMR (151MHz, Chloroform-d) δ198.4,166.5,140.0,132.9,130.2,129.5,128.5,128.3,128.3,126.3,64.3,45.5,31.4,28.4,27.7,26.2.

[0203] Example 48:

[0204]

[0205] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with (4-methylpent-3-en-1-yl)benzene (40.0 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 60%. 1 H NMR(600MHz,Chloroform-d)δ7.30(t,J=6.0Hz,4H),7.23–7.19(m,4H),7.17(d,J=6.0Hz,2H),3.62–3.58(m,1H),3.02(t,J=9. 0Hz,2H),2.92(t,J=9.0Hz,2H),2.74–2.69(m,1H),2.61–2.56(m,1H),1.98–1.88(m,2H),1.82–1.75(m,1H),0.93–0.91(m,6H). 13 C NMR (151MHz, Chloroform-d) δ198.6,141.9,140.1,128.5,128.4,128.3,128.2,126.3,125.8,50.6,45.7,34.7,33.6,32.3,31.7,19.9,18.6.

[0206] Example 49:

[0207]

[0208] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with cyclooctene (27.5 mg, 0.25 mmol), yielding a colorless oily liquid in 30% yield. 1 H NMR(600MHz,Chloroform-d)δ7.29(t,J=9.0Hz,2H),7.22–7.18(m,3H),3.74–3.70(m,1H),2.97( t,J=9.0Hz,2H),2.82(d,J=6.0Hz,2H),1.95–1.90(m,2H),1.72–1.65(m,4H),1.62–1.51(m,8H). 13 C NMR (151MHz, Chloroform-d) δ198.7,140.2,128.5,128.3,126.2,45.5,43.8,32.2,31.5,27.1,25.6,25.2.

[0209] Example 50:

[0210]

[0211] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 2-phenyl-1-propene (29.5 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 30%. 1 H NMR (600MHz, Chloroform-d) δ7.33–7.28(m,4H),7.25–7.18(m,6H),3.17–3.11(m,2H),2.98–2.91(m,3H),2.85(t,J=9.0Hz,2H),1.33(d,J=6.0Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ198.4,145.0,140.0,128.5,128.4,128.3,127.0,126.6,126.3,45.5,39.8,36.6,31.5,20.8.

[0212] Example 51:

[0213]

[0214] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with p-tert-butylstyrene (40.0 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 36%. 1H NMR(600MHz,Chloroform-d)δ7.34–7.29(m,4H),7.23–7.19(m,3H),7.15(d,J=6.0Hz,2H),3.12( d,J=9.0Hz,2H),2.99(t,J=9.0Hz,2H),2.88(t,J=9.0Hz,2H),2.84(t,J=9.0Hz,2H),1.32(s,9H). 13 C NMR (151MHz, Chloroform-d) δ198.5,149.3,140.1,136.9,128.5,128.3,128.2,126.3,125.4,45.6,35.3,34.4,31.4,31.4,30.3.

[0215] Example 52:

[0216]

[0217] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with N,N-diphenylacrylamide (55.8 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 51%. 1 H NMR(600MHz,Chloroform-d)δ7.40–7.33(m,5H),7.27–7.24(m,6H),7.20–7.14(m,4H),3 .17(t,J=6.0Hz,2H),2.94(t,J=9.0Hz,2H),2.82(t,J=6.0Hz,2H),2.54(t,J=6.0Hz,2H). 13 C NMR (151MHz, Chloroform-d) δ198.6,170.9,142.3,140.0,129.8,128.8,128.5,128.4,128.2,126.3,45.3,35.5,31.3,24.6.

[0218] Example 53:

[0219]

[0220] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 5-methyl-2-(prop-1-en-2-yl)cyclohexylbenzoate (64.5 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 52%. 1H NMR(600MHz,Chloroform-d)δ8.06–8.03(m,2H),7.57–7.53(m,1H),7.46–7.42(m,2H),7.26–7.24 (m,1H),7.21–7.16(m,2H),7.14–7.11(m,2H),5.05–4.97(m,1H),3.07–3.03(m,1H),3.00–2.95(m ,1H),2.90–2.85(m,2H),2.81–2.76(m,2H),2.72–2.66(m,1H),2.21–2.16(m,1H),1.89–1.83(m,1 H),1.78–1.71(m,3H),1.62–1.54(m,1H),1.32–1.21(m,1H),1.13–1.04(m,1H),0.97–0.93(m,6H). 13 C NMR(151MHz,Chloroform-d)δ198.3,165.8,140.1,132.7,130.7,129.5,128.4,128.3 ,128.3,126.2,74.3,46.3,45.4,40.8,34.7,34.3,33.0,31.3,31.2,26.7,21.9,16.5.

[0221] Example 54:

[0222]

[0223] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with dihydrocarvone (30.2 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 64%. 1 H NMR(600MHz,Chloroform-d)δ(mixture of two diastereomers)7.29–7.26(m,2H),7.21–7.17(m,3H),3.04–3.00(m,1H),2.9 7(t,J=6.0Hz,2H),2.87–2.85(m,2H),2.75–2.68(m,1H),2.38–2.30(m,2H),2 .18–2.06(m,2H),1.87–1.81(m,1H),1.79–1.71(m,1H),1.67–1.57(m,1H),1. 56–1.44(m,1H),1.34–1.25(m,1H),1.02(d,J=6.0Hz,3H),0.94–0.91(m,3H). 13C NMR(151MHz,Chloroform-d)δ212.7,212.6,198.3,140.0,128.5,128.3,126.3,126.2,45.9,45.5,4 4.9,44.8,44.1,43.9,43.8,38.1,38.0,34.7,33.3,33.1,31.4,29.6,27.3,15.6,15.5,14.3,14.2.

[0224] Example 55:

[0225]

[0226] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with levo-beta-pinene (34.0 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 75%.

[0227] Nuclear magnetic resonance data: 1 H NMR(600MHz,Chloroform-d)δ7.29(t,J=6.0Hz,2H),7.22–7.18(m,3H),2.99–2.96(m,4H),2.87–2.84(m,2 H),2.37–2.32(m,1H),2.18–2.12(m,1H),2.02–1.81(m,6H),1.51–1.45(m,1H),1.19(s,3H),1.05(s,3H). 13 C NMR (151MHz, Chloroform-d) δ198.8,140.1,128.5,128.3,126.3,45.5,45.3,41.2,41.1,38.6,35.5,33.3,31.5,27.9,26.1,23.1,21.7.

[0228] Example 56:

[0229]

[0230] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with camphene (34.0 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 67%. 1H NMR(600MHz,Chloroform-d)δ7.29(t,J=6.0Hz,2H),7.20(d,J=9.0Hz,3H),3.00–2.94(m,3H),2.88–2.84(m,3H), 2.17(s,1H),1.77(s,1H),1.62–1.55(m,3H),1.35–1.24(m,3H),1.18(d,J=12.0Hz,1H),0.98(s,3H),0.88(s,3H). 13 C NMR (151MHz, Chloroform-d) δ198.7,140.1,128.5,128.3,126.3,49.8,49.2,45.5,41.7,37.6,36.9,32.2,31.5,27.3,24.6,21.1,20.0.

[0231] Example 57:

[0232]

[0233] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with terpineone (54.5 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 75%. 1 H NMR(600MHz,Chloroform-d)δ(mixture of two diastereomers)7.29–7.27(m,2H),7.21–7.18(m,3H),5.74(s,1H),3.06–3.01(m,1H),3. 00–2.97(m,2H),2.89–2.87(m,2H),2.82–2.72(m,1H),2.48–2.39(m,1H),2.36–3.32(m,1 H),2.30–2.20(m,2H),2.01–1.95(m,1H),1.90–1.81(m,2H),1.75–1.69(m,1H),1.60–1.5 2(m,1H),1.22–1.10(m,1H),1.05(d,J=6.0Hz,3H),1.02–0.94(m,4H),0.91–0.90(m,3H). 13C NMR(151MHz,Chloroform-d)δ199.5,198.4,198.3,170.6,140.0,128.4,128.2,126.3,124.5,124.4,45.5,45.4,42.9,42.0, 40.5,40.4,40.3,39.3,39.1,37.9,37.8,36.5,36.4,33.7,33.3,33.0,32.8,31.4,30.5,28.4,16.8,15.7,15.6,14.9,14.8.

[0234] Example 58:

[0235]

[0236] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 4-([1,1'-biphenyl]-4-yl)-4-oxobutyrate (80.5 mg, 0.25 mmol), yielding a colorless oily liquid with a yield of 61%. 1 H NMR(600MHz,Chloroform-d)δ8.07(d,J=6.0Hz,2H),7.69(d,J=6.0Hz,2H),7.63(d,J=6.0H z,2H),7.48(t,J=9.0Hz,2H),7.41(t,J=6.0Hz,1H),7.29(t,J=6.0Hz,2H),7.22–7.18(m,3 H),4.22–4.13(M,2H),3.35(t,J=6.0Hz,2H),3.00–2.94(m,3H),2.89–2.86(m,2H),2.85–2 .79(m,3H),1.86–1.80(m,1H),1.78–1.73(m,1H),1.54–1.49(m,1H),0.98(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ198.1,197.5,172.7,145.7,139.9,139.7,135.1,128.8,128.5,1 28.4,128.2,128.1,127.1,127.0,126.2,62.5,45.4,35.3,34.2,33.3,31.4,30.4,28.2,18.8.

[0237] Example 59:

[0238]

[0239] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 2-(10-oxo-10,11-dihydrodibenzo[b,f]thiacin-2-yl)propionate (91.5 mg, 0.25 mmol), yielding a colorless oily liquid in 61% yield. 1 H NMR(600MHz,Chloroform-d)δ(mixture oftwo diastereomers)8.19(d,J=6.0Hz,1H),7.58–7.56(m,2H),7.40–7.37(m,2H),7.30 –7.25(m,3H),7.19–7.16(m,3H),7.14(d,J=6.0Hz,1H),4.34(s,2H),4.13–4.04(m ,2H),3.72–3.68(m,1H),2.96(t,J=9.0Hz,2H),2.85–2.81(m,3H),2.72–2.68(m,1 H),1.67–1.60(m,2H),1.47(d,J=6.0Hz,3H),1.43–1.36(m,1H),0.86–0.83(m,3H). 13 C NMR(151MHz,Chloroform-d)δ198.1,191.1,173.7,142.6,142.5,140.1,139.9,137.8,136.0,133.1,132.4,131.4,131.3,130.7,128. 6,128.5,128.4,128.2,126.7,126.3,126.2,62.9,62.8,50.9,45.4,45.1,35.2,35.1,34.1,31.4,30.4,30.3,18.7,18.6,18.2,18.1.

[0240] Example 60:

[0241]

[0242] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with (8R,9S,13S,14S)-13-methyl-3-((2-methylallyl)oxy)-6,7,8,9,11,12,13,14,15,16-decylhydro-17H-cyclopentan[a]phenanthrene-17-one (81.1 mg, 0.25 mmol), yielding a colorless oily liquid in 57% yield. 1H NMR(600MHz,Chloroform-d)δ7.29(t,J=6.0Hz,2H),7.22–7.19(m,4H),6.73–6.70(m,1H),6. 65–6.61(m,1H),3.83–3.78(m,2H),3.12–3.09(m,1H),3.00–2.96(m,3H),2.92–2.87(m,4H),2 .53–2.49(m,1H),2.42–2.39(m,1H),2.28–2.24(m,1H),2.18–2.12(m,2H),2.08–2.00(m,2H) ,1.97–1.95(m,1H),1.71–1.49(m,5H),1.47–1.41(m,1H),1.07(d,J=6.0Hz,3H),0.92(s,3H). 13 C NMR(151MHz,Chloroform-d)δ198.3,156.9,140.0,137.7,132.1,128.5,128.3,126.3,126.2,114.5,112 .1,71.2,50.3,47.9,45.5,43.9,38.3,35.8,33.7,32.1,31.5,31.4,29.6,26.5,25.9,21.5,16.3,13.8.

[0243] Example 61:

[0244]

[0245] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with citronellol acetate (49.5 mg, 0.25 mmol), resulting in a colorless oily liquid with a yield of 56%. 1 H NMR(600MHz,Chloroform-d)δ(mixture of two diastereomers)7.29–7.25(m,2H),7.21–7.16(m,3H),4.10–4.02(m,2H),3.49–3.44(m,1H),2.99–2.95(m,2H),2.88–2.84(m,2H ),2.03(s,3H),1.95–1.86(m,1H),1.66–1.58(m,2H),1.54–1.48(m,1H),1.45–1.35(m,2H),1.34–1.13(m,2H),0.90–0.86(m,9H). 13C NMR(151MHz,Chloroform-d)δ198.7,198.6,171.2,140.1,128.4,128.3,128.2,126.2,62.8,62.7,51.0,50.9,4 5.7,35.4,35.2,34.3,34.2,32.1,31.8,31.6,29.9,29.7,29.6,29.5,21.0,20.1,20.0,19.5,19.3,18.6,18.5.

[0246] Example 62:

[0247]

[0248] The experimental procedure was the same as in Example 32, except that (3-methylbut-3-en-1-yl)benzene was replaced with 3-methylbut-3-en-1-yl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate (106.3 mg, 0.25 mmol), yielding a colorless oily liquid in 63% yield. 1 H NMR(600MHz,Chloroform-d)δ7.64(d,J=6.0Hz,2H),7.45(d,J=12.0Hz,2H),7.27(t,J=9 .0Hz,2H),7.20–7.16(m,3H),6.96(s,1H),6.86(d,J=6.0Hz,1H),6.67–6.65(m,1H),4.1 8–4.09(m,2H),3.82(s,3H),3.66(s,2H),2.95(t,J=6.0Hz,2H),2.89–2.83(m,3H),2.76 –2.73(m,1H),2.38(s,3H),1.75–1.67(m,2H),1.49–1.43(m,1H),0.90(d,J=6.0Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ198.1,170.7,168.1,155.9,139.9,139.1,135.8,133.8,131.1,130.1,130.5,129 .0,128.4,128.2,126.2,114.9,112.5,111.5,101.1,62.9,55.6,45.4,35.2,34.2,31.3,30.5,30.3,18.8,13.3.

[0249] Comparative Examples 1-6: Study on the Dosage of Tetrabutylammonium Dectungstate Photocatalyst

[0250] Except for replacing the amount of photocatalyst tetrabutylammonium decatungstate in Example 1 (41.5 mg, 0.0125 mmol) with other contents as shown below, all other operations were exactly the same, thus repeating Example 1 to obtain Comparative Examples 1-6. The amount of photocatalyst used and the product yield are shown in Table 1 below.

[0251] Table 1

[0252] serial number Dosage of tetrabutylammonium decatungstate (mmol) Corresponding Implementation Examples Product yield (%) Comparative Example 1 0.0150 Example 1 79 Comparative Example 2 0.0125 Example 1 87 Comparative Example 3 0.0100 Example 1 80 Comparative Example 4 0.0075 Example 1 80 Comparative Example 5 0.0050 Example 1 71 Comparative Example 6 0.0025 Example 1 45

[0253] As can be seen from the data in Table 1, the optimal dosage of the photocatalyst tetrabutylammonium decatungstate is 0.0125 mmol.

[0254] Comparative Examples 7-11: Study on S8 Dosage

[0255] Except for changing the amount of S8 in Example 1, all other operations were exactly the same, thus repeating Example 1 to obtain Comparative Examples 7-11. The amount of S8 used and the product yield are shown in Table 2 below.

[0256] Table 2

[0257] serial number [S8 amount (mmol)] Corresponding Implementation Examples Product yield (%) Comparative Example 7 0.0625 Example 1 63 Comparative Example 8 0.0875 Example 1 78 Comparative Example 9 0.1125 Example 1 85 Comparative Example 10 0.1375 Example 1 81 Comparative Example 11 0.1625 Example 1 79

[0258] Therefore, the optimal amount of S8 in this reaction is 0.1125 mmol.

[0259] Comparative Examples 12-17: Study on the Dosage of Phenylacetol in Formula (I)

[0260] Except for changing the amount of phenylpropanol of formula (I) in Example 1, all other operations were exactly the same, thus repeating Example 1 to obtain Comparative Examples 12-17. The amount of phenylpropanol of formula (I) used and the product yield are shown in Table 3 below.

[0261] Table 3

[0262] serial number Formula (I) Amount of phenylpropanol (mmol) Corresponding Implementation Examples Product yield (%) Comparative Example 12 1.125 Example 1 81 Comparative Example 13 1.000 Example 1 82 Comparative Example 14 0.8750 Example 1 86 Comparative Example 15 0.7500 Example 1 80 Comparative Example 16 0.6250 Example 1 80 Comparative Example 17 0.5000 Example 1 72

[0263] Therefore, the optimal amount of phenylpropanol of formula (I) in this reaction is 0.8750 mmol.

[0264] Comparative Examples 18-23: Study on the Amount of Solvent Acetonitrile

[0265] Except for changing the amount of solvent acetonitrile in Example 1, all other operations were exactly the same, thus repeating Example 1 to obtain Comparative Examples 18-23. The amount of solvent acetonitrile used and the product yield are shown in Table 4 below.

[0266] Table 4

[0267]

[0268]

[0269] Considering the solubility of formulas (I), (II) and (III), the optimal amount of solvent acetonitrile in this reaction is 0.50 mL.

[0270] Comparative Examples 24-29: Studies on the sensitivity of standard responses

[0271] Except for changing the reaction conditions in Example 1, all other operations were exactly the same, thus repeating Example 1 to obtain Comparative Examples 24-29. The changed conditions and product yields are shown in Table 5 below.

[0272] Table 5

[0273] serial number Conditions for change Corresponding Implementation Examples Product yield (%) Comparative Example 24 None (standard conditions) Example 1 84 Comparative Example 25 No photocatalyst added Example 1 0 Comparative Example 26 No lighting Example 1 0 Comparative Example 27 Use 455nm blue LED light Example 1 0 Comparative Example 28 Add 2.0 equivalents of water Example 1 77 Comparative Example 29 The reaction takes place in the air. Example 1 31

[0274] This shows that the reaction cannot proceed smoothly without a photocatalyst or near-ultraviolet LED light, has good compatibility with small amounts of water, but poor tolerance to air.

[0275] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for photocatalytic synthesis of thioester compounds, characterized in that, Includes the following steps: In an inert gas atmosphere and an organic solvent, the compound shown in formula (I), the element shown in formula (II), and the compound shown in formula (III) undergo hydrogen transfer and coupling reactions under the condition of a photocatalyst to obtain the thioester compound shown in formula (IV). R 1 Selected from one or more of alkyl, aryl, and heteroaryl groups; R 2 R 3 R 4 Each group is independently selected from one or more of hydrogen, alkyl, aryl, ester, cyclic ketone, amide, and heterocyclic groups.

2. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, R 1 Selected from C 1-18 Alkyl, C 6-12 One or more of aryl and 5-10 heteroaryl groups; wherein, each of the above R 1 The alkyl, aryl, or heteroaryl groups are optionally replaced by one or more groups selected from halogen, ester, hydroxyl, C 1-6 Alkyl, phenyl, aryloxy, 5-6 membered heteroaryl, C 3-6 Cycloalkyl substituted; R 2 R 3 R 4 Selected independently from hydrogen and C 1-24 Alkyl, C 6-12 Aryl, 5-12 heteroaryl, C 3-12 One or more of cycloalkyl, cycloketyl, and 3-12 membered heterocyclic groups; wherein, the above R 2 R 3 R 4 The alkyl, aryl, heteroaryl, cycloalkyl, and heterocyclic groups are optionally separated by one or more C14 groups. 1-6 Alkyl, phenyl, 5-6 membered heteroaryl, C 3-6 Cycloalkyl, alkoxy, aryloxy, arylate, 5-6 membered heterocyclic groups, -C(=O)R 3a -OC(=O)R 3a -C(=O)NR 3b R 3c or -OC(=O)NR 3b R 3c Replaced; or R 3 and R 4 Connect them together to form a 3-12 elemental ring; or R 2 and R 3 Connect them together to form a 5-12 elemental ring; Among them, R 3a R 3b R 3c Selected independently from C 1-12 Alkyl, alkenyl, C 3-12 cycloalkyl, C 6-12 One or more of aryl and 5-12 heteroaryl groups; wherein, the above R 3a R 3b R 3c The alkyl, alkenyl, cycloalkyl, aryl, and heteroaryl groups are optionally bonded by one or more hydroxyl groups, halogens, or C-terminal groups. 1-6 Alkyl, carbonyl biphenyl, heterocyclic, and heteroaryl groups are substituted; or R 3b With R 3c They connect together to form 3-6 membered heterocyclic groups.

3. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The compound represented by formula (I) has one of the following structural formulas:

4. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The compound represented by formula (III) has one of the following structural formulas:

5. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The compound represented by formula (IV) has one of the following structural formulas:

6. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The photocatalyst is a tungstate.

7. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The molar ratio of the compound shown in formula (I) to the compound shown in formula (III) is (1.5 to 5):

1.

8. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The reaction temperature for the hydrogen transfer and coupling reaction is 35–40 °C.

9. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The molar ratio of the element shown in formula (II) to the compound shown in formula (III) is 1:2.

2.

10. The method for photocatalytic synthesis of thioester compounds according to claim 1, characterized in that, The organic solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, methanol, and dichloromethane.

Images