A copper catalyst, its preparation method and use

Abstract

This invention discloses a copper catalyst, its preparation method, and its applications. Specifically, this invention provides a copper catalyst prepared by the following method: mixing copper salt, coffee grounds, and a solvent, followed by centrifugation and calcination to obtain the copper catalyst. This invention uses inexpensive household waste, coffee grounds, to support copper in the preparation of a heterogeneous copper catalyst. The preparation is convenient, simple, low-cost, and environmentally friendly. Furthermore, the catalyst exhibits excellent performance and is applicable to a wide range of compounds.

Description

Technical Field

[0001] This invention relates to a copper catalyst, its preparation method, and its application. Background Technology

[0002] CN bonds are widely found in biomolecules and organic compounds, such as amino acids, proteins, DNA, and many drugs. The strength and properties of this bond make it play an important role in organic chemistry and biochemistry.

[0003] (1) Role in biomolecules:

[0004] Amino acids: Amino acids are the basic building blocks of proteins. The C-N bond connects the amino group and carboxyl group of an amino acid to form a peptide chain.

[0005] Proteins: The structure of proteins contains a large number of CN bonds, which determine the spatial configuration and function of proteins.

[0006] (2) Application in pharmaceuticals:

[0007] Many drug molecules also contain CN bonds, such as those found in antibiotics, anticancer drugs, and neurotransmitters. The presence of these bonds can affect the drug's activity, stability, and metabolic pathways.

[0008] (3) Importance in organic synthesis:

[0009] In the field of organic synthesis, the construction of CN bonds is a key step in many reactions, such as imine and amination reactions, which are of great significance for the synthesis of complex organic molecules.

[0010] There are many methods for constructing CN bonds, such as amination, iminolation, and coupling reactions. Among these, transition metal-catalyzed NH bond insertion of carbenes is a very powerful method for constructing CN bonds. Although homogeneous catalysts have relatively high catalytic activity, they also suffer from low selectivity and difficulty in separation. Heterogeneous catalysts, on the other hand, are widely studied due to their high activity, high selectivity, recyclability, and ease of separation.

[0011] Despite the challenges of heterogeneous catalysis, such as complex preparation, harsh reaction conditions, and environmental unfriendliness, it still holds broad application prospects. Future research will focus on milder reaction conditions, green catalysis technologies, and industrial applications of heterogeneous catalysts. Through continuous research and innovation, we aim to promote the development and application of heterogeneous catalysis technology, improve reaction rates, reduce environmental impact, and promote sustainable development. Summary of the Invention

[0012] The technical problem to be solved by the present invention is to overcome the defects of the prior art in the preparation of heterogeneous catalysts, such as complex preparation, harsh reaction conditions, high cost and environmental unfriendliness, and to provide a heterogeneous copper catalyst that is easy to prepare, has ultra-low cost, is environmentally friendly and has high versatility.

[0013] The present invention solves the above-mentioned technical problems through the following technical solution:

[0014] The present invention provides a copper catalyst comprising carbonized coffee grounds and copper ions, wherein the copper is supported on the carbonized coffee grounds; the copper comprises monovalent copper ions and divalent copper ions; preferably, the copper catalyst is composed of the carbonized coffee grounds and the copper; the copper ions are composed of monovalent copper ions and divalent copper ions.

[0015] Copper ions are loaded onto coffee grounds and combine with the coordinating atoms of the coffee grounds to form a stable catalyst.

[0016] The present invention also provides a copper catalyst, which is prepared by the following method, comprising the following steps:

[0017] The copper catalyst was obtained by mixing copper salt, coffee grounds and solvent, centrifuging and calcining.

[0018] In some embodiments, the copper salt is a divalent copper salt; such as one or more of copper chloride, copper sulfate, copper nitrate, and copper acetate; for example, copper chloride.

[0019] The coffee grounds mentioned are regular coffee grounds, such as those purchased from FamilyMart convenience stores.

[0020] In some embodiments, the mass ratio of the copper salt to the coffee grounds is (0.01-0.3):1; for example, (0.1-0.3):1; for example, 0.21:1.

[0021] In some embodiments, the solvent is one or more of water, methanol, and ethanol; for example, water; the water is, for example, deionized water.

[0022] In some embodiments, the mass-to-volume ratio of the coffee grounds and the solvent is 1 g / (10-30 ml); for example, 1 g / 20 ml.

[0023] In some embodiments, the mixing is agitation or ultrasonic mixing, such as ultrasonic mixing.

[0024] In some implementations, the mixing time is 20-40 minutes, for example, 30 minutes.

[0025] In some embodiments, a drying step is included before calcination; the drying may be vacuum pump drying, and the drying time may be 5-7 hours; for example, 6 hours.

[0026] In some embodiments, the calcination temperature is 600-800°C; for example, 700°C.

[0027] In some embodiments, the calcination is carried out at a heating rate of 4-6°C / min to the calcination temperature and then held; for example, at a heating rate of 5°C / min to the calcination temperature and then held.

[0028] In some implementations, the calcination time is 2-4 hours; for example, 3 hours.

[0029] In some embodiments, the calcination is carried out under a protective atmosphere, such as an argon atmosphere.

[0030] In some implementations, the calcination is carried out in a tubular furnace.

[0031] In some embodiments, the copper catalyst is obtained by naturally cooling to room temperature after calcination.

[0032] In some embodiments, the preparation method of the copper catalyst includes the following specific steps: ultrasonically mixing water, (0.1-0.3) equivalents of copper chloride and 1 equivalent of coffee grounds, centrifuging, drying, and calcining at 700°C under a protective atmosphere to obtain the copper catalyst.

[0033] In some embodiments, the copper catalyst is used to catalyze the following coupling reaction:

[0034] Include Fragment amine and containing The fragment reacts to form a diazo compound. ;

[0035] Or; containing Fragment alcohol and containing The fragment reacts to form a diazo compound. .

[0036] In some implementations, the containing The diazo compound of the fragment is a compound of formula I; the containing The amine of the fragment is a compound of formula II; the containing The alcohol fragment is a compound of formula IV;

[0037] The copper catalyst catalyzes the following coupling reactions: the coupling reaction of compound I and compound II to generate compound III; or the coupling reaction of compound I and compound IV to generate compound V;

[0038] ;

[0039] ;

[0040] Among them, R 1 -COOR 1-1 R 1-1 C 1-6 Alkyl or C 1-6 alkenyl;

[0041] R 2 For H, C 6-14 aryl, 5-6 membered heteroaryl, with one or more R 2-1 Replacement C 6-14 aryl or aryl with one or more R 2-2 Substituted 5-6 aryl groups; R 2-1 and R 2-2 C independently 1-6 Alkyl, C 1-6 Alkoxy, halogen or C 1-6 Halogenated alkyl groups;

[0042] R 3 C 1-6 Alkyl, C 6-14 aryl, with one or more R 3-1 Replacement C 1-6 Alkyl or with one or more R 3-2 Replacement C 6-14 Aryl; R 3-1 and R 3-2 Selected independently from C 6-14 Aryl, 5-15 membered heteroaryl, 5-10 membered heterocycloalkyl, C 5-7 Cycloalkenyl, C 1-6 Alkyl, C 1-6 Alkyl groups and those with one or more R groups 3-1-1 Replacement C 6-14 Aryl; R 3-1-1 C 1-6 Alkyl, C 1-6 Alkoxy, halogen or C 1-6 Halogenated alkyl groups;

[0043] R 4 For H or C 1-6 alkyl;

[0044] Or, R 3 R 4 It forms 5-10 membered heterocyclic alkyl groups, 5-15 membered heteroaryl groups with the N atoms therein, and is bonded by one or more R atoms. 4-1 Substituted 5-10 membered heterocyclic alkyl groups, with one or more R 4-2 Substituted 5-15 aryl groups or ;R 4-1 and R 4-2 Selected independently from C6-10 Aryl, 5-15 quinone heteroaryl, C 1-6 Alkyl, oxy, and one or more R 4-1-1 Replacement C 6-10 aryl, with one or more R 4-1-2 Substituted 5-15 aryl groups and one or more R 4-1-3 Replacement C 1-6 Alkyl; R 4-1-1 R 4-1-2 and R 4-1-3 Selected independently from -SR 4-1-1-1 C 6-10 aryl, with one or more R 4-1-1-2 Replacement C 6-10 aryl and -OR 4 -1-1-3 Ring A is a 5-10 membered heterocyclic alkyl group; ring B is formed by one or more R groups. 4-1-1-4 Substituted 5-15 aryl groups; R 4-1-1-1 and R 4 -1-1-3 Selected independently from C 6-10 aryl, 5-15 quinone heteroaryl and one or more C 1-6 Alkyl-substituted C 6-10 Aryl; R 4 -1-1-2 and R 4-1-1-4 Each is a halogen, independent of the others;

[0045] R 5 C 1-6 Alkyl, C 6-14 Aryl, 5-15 quinone heteroaryl, C 5-18 cycloalkyl, C 5-18 Cycloalkenyl, 5-10 membered heterocyclic alkyl, with one or more R 5-1 Substituted C1-6 alkyl, with one or more R 5-2 Replacement C 5-18 cycloalkyl, with one or more R 5-3 Replacement C 5-18 Cycloalkenyl or with one or more R 5-4 Substituted 5-10 membered heterocyclic alkyl groups; R 5-1 -R 5-4 Selected independently from C 1-8 Alkyl, C 6-14 Aryl, -COO-C 1-6 Alkyl, 5-15-membered heteroaryl, with one or more R 5-1-1 Replacement C 1-6 Alkyl group, by one or more R 5-1-2 Replacement C 6-14 aryl, with one or more R5-1-3 Substituted 5-10 membered heterocyclic alkyl groups and NR 5-1-4 R 5-1-5 ;R 5-1-1 -R 5-1-5 Selected independently from C 6-14 Aryl, halogen and C 1-6 Alkyl group.

[0046] In some implementation schemes, R 1 For COOMe, COOEt, COOBn or .

[0047] In some implementation schemes, R 2 For Ph, , , , , , , , , Or H.

[0048] In some implementation schemes, R 3 for , , , , , , , , , , , , , , , , , , or .

[0049] In some implementation schemes, R 4 It can be H or Me.

[0050] In some implementation schemes, R 3 R 4 Forming with the N atoms in between , , , , , or .

[0051] In some implementation schemes, R 5 for , , , , , , , , , , , , , or .

[0052] In some embodiments, the compound of formula I is , , , , , , , , , , , or .

[0053] In some embodiments, the compound of formula II is , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0054] In some embodiments, the compound of formula IV is , , , , , , , , , , , , , or .

[0055] In some embodiments, the compound of formula III is , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0056] In some embodiments, the compound of formula V is , , , , , , , , , , , , , or .

[0057] In some embodiments, in the coupling reaction, the containing The fragment of the diazo compound and the containing The molar ratio of the amine fragments is (0.8-1.2):1; for example, 1:1.

[0058] In some embodiments, in the coupling reaction, the containing Fragments of diazo compounds and containing The molar ratio of the alcohol in the fragment is (1.5-2.5):1; for example, 2:1.

[0059] In some embodiments, in the coupling reaction, the copper catalyst and the catalyst containing... The mass-to-molar ratio of the diazo compound in the fragment is (15-25) g / 1 mol; for example, 20 g / 1 mol.

[0060] The coupling reaction also includes a solvent, which can be a conventional solvent for this type of reaction in the art, preferably a haloalkanes solvent; for example, DCE.

[0061] In some embodiments, the coupling reaction is carried out at a temperature of 50-70°C; for example, 60°C.

[0062] In some embodiments, the coupling reaction is carried out under a protective atmosphere; for example, under a nitrogen atmosphere.

[0063] The progress of the coupling reaction can be monitored using conventional detection methods in the art (e.g., HPLC, TLC, or NMR), generally with a concentration of... The reaction ends when the diazo compound in the fragment disappears. The reaction time is generally 8-16 hours, for example, 12 hours.

[0064] In some embodiments, the reactants in the coupling reaction consist of the following components: the... The fragment of the diazo compound, the one containing Fragment of amine or the contained The fragment of alcohol, the copper catalyst, and the solvent.

[0065] This invention also provides a method for preparing a copper catalyst, characterized by comprising the following steps:

[0066] The copper catalyst was obtained by ultrasonication, centrifugation, and calcination of a mixture of copper salt, coffee grounds, and solvent.

[0067] The conditions and procedures for the steps are as described in the preceding item; the definitions of the copper salt, coffee grounds, and solvent are as described in the preceding item.

[0068] The present invention also provides the application of any of the aforementioned copper catalysts in a catalytic coupling reaction, wherein the conditions and operation of the coupling reaction are as described in any of the preceding claims.

[0069] The present invention also provides the following compounds:

[0070] .

[0071] Unless otherwise specified, the terms used in this invention have the following meanings:

[0072] When listing numerical ranges, each value and subranges within that range are included by default. For example, "C1-6" includes C1, C2, C3, C4, C5, C6, C1-6, C1-5, C1-4, C1-3, C1-2, C2-6, C2-5, C2-4, C2-3, C3-6, C3-5, C3-4, C4-6, C4-5, and C5-6 alkyl groups.

[0073] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0074] The term "alkyl" refers to a straight-chain or branched alkyl group having a specified number of carbon atoms (e.g., C1-8 or C1-6). Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0075] The term "halogenated alkyl" refers to an "alkyl" that has been substituted with one or more "halogens"; for example, CF3.

[0076] The term "cycloalkyl" refers to a saturated cyclic group consisting of only carbon atoms, having a specified number of carbon atoms (e.g., C3-6). It can be a monocyclic, bridged, or spirocyclic group, and each ring is saturated.

[0077] The term "cycloalkenyl" refers to a cyclic group consisting of only carbon atoms (e.g., C5-7) and containing one or more olefinic bonds; for example, cyclopentenyl, cyclohexenyl, or cycloheptenyl.

[0078] The term "heterocyclic alkyl" refers to a cyclic group having a specified number of ring atoms (e.g., 5-10; for example, 5-9, 5-8, or 5-6), a specified number of heteroatoms (e.g., 1, 2, or 3), and a specified type of heteroatom (1, 2, or 3 of N, O, and S), which can be monocyclic, bridged, or spirocyclic, and each ring is saturated. A bridged ring is a polycyclic ring that shares two or more atoms between monocyclic rings. A spirocyclic ring is a polycyclic ring that shares one atom between monocyclic rings. Heterocyclic alkyl groups include, but are not limited to, nitrogen-containing heterocyclic butyl, tetrahydropyrrolyl, tetrahydrofuranyl, morpholinyl, and piperidinyl.

[0079] The term "aryl" refers to an aryl group having a specified number of carbon atoms (e.g., C6-). 14 For example, C6- 10 An aryl group is a cyclic group consisting solely of carbon atoms, which can be monocyclic or polycyclic, and at least one ring is aromatic (following Hückel's rule). The aryl group is linked to other segments of the molecule via an aromatic or non-aromatic ring. Aryl groups include, but are not limited to, phenyl, naphthyl, and benzocyclohexyl.

[0080] The term "heteroaryl" refers to a cyclic group having a specified number of ring atoms (e.g., 5-15, 5-10, or 5-6), a specified number of heteroatoms (e.g., 1, 2, or 3), and a specified type of heteroatom (1, 2, or 3 of N, O, and S). It can be monocyclic or polycyclic, and at least one ring must be aromatic (conforming to Hückel's rule). Heteroaryl groups are linked to other segments of a molecule via aromatic or non-aromatic rings. Heteroaryl groups include, but are not limited to, furanyl, pyrroleyl, thiopheneyl, pyrazolyl, imidazoyl, oxazolyl, thiazoyl, pyridinyl, pyrimidinyl, and indoleyl groups.

[0081] The term "multiple" refers to 2, 3, 4, or 5.

[0082] When any variable (e.g., group R) 1-1 When these terms appear multiple times in the definition of a compound, their definitions are independent and do not affect each other. For example, a compound defined by three R's... 1-1 Replacement C6- 10 Aryl refers to C6- 10 Aromatic compounds will be 3 R 1-1 Replace, 3 R 1-1 The definitions are independent of each other and do not affect each other.

[0083] The positive and progressive effects of this invention are as follows: a heterogeneous copper catalyst is prepared by loading copper onto inexpensive household waste coffee grounds. The preparation is convenient, simple to operate, low in cost and environmentally friendly. Furthermore, the catalyst has excellent performance and is applicable to a wide range of compounds. Detailed Implementation

[0084] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0085] Example 1

[0086] 210 mg of anhydrous copper chloride, 1 g of coffee grounds (purchased from FamilyMart), and 20 mL of deionized water were mixed in a 40 mL Vial bottle. After sonication for 30 min, the mixture was centrifuged, vacuum pumped for 6 hours, and then transferred to a tube furnace for calcination. The furnace calcination conditions were: 5... o C / min is the heating rate up to 700 oAfter being kept in an argon atmosphere for 3 hours, the copper supported on coffee grounds is obtained by naturally cooling to room temperature, i.e., copper / coffee grounds catalyst.

[0087] Example 2: The reaction of carbene insertion into aromatic amines to form CN bonds using a copper / coffee grounds catalyst, specifically including the following process:

[0088] ;

[0089] Under a nitrogen atmosphere, 2 mg of the copper / coffee grounds catalyst prepared in Example 1 was weighed, followed by 0.5 mL of DCE, and then 0.1 mmol of methyl diazophenylacetate (1) and 0.1 mmol of benzylamine (2). The mixture was sealed and stirred at 60 °C for 12 h. After the reaction was completed and the temperature was lowered to room temperature, the catalyst was filtered off, and 1,3,5-trimethoxybenzene was added as an internal standard. After rotary evaporation, deuterated chloroform was added for nuclear magnetic resonance (NMR) to confirm a yield of 96%. After purification by silica gel column chromatography, the pure product was obtained, and the NMR shift was consistent with that of the standard.

[0090] The NMR data for product P1 are as follows:

[0091] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.41 – 7.23 (m, 10H), 4.40 (s, 1H), 3.73 (d, J = 2.4 Hz, 2H), 3.69 (s, 3H).

[0092] 13 C-NMR (126 MHz, CDCl3): δ 173.57, 139.54, 138.12, 128.87, 128.57,128.47, 128.28, 127.71, 127.30, 64.43, 52.40, 51.45.

[0093] Example 3: The reaction of carbene insertion into heterocyclic amines to form CN bonds using a copper / coffee grounds catalyst, specifically including the following process:

[0094] ;

[0095] Under a nitrogen atmosphere, 2 mg of the copper / coffee grounds catalyst prepared in Example 1 was weighed, followed by 0.5 mL of DCE, and then 0.1 mmol of methyl diazophenylacetate (1) and 0.1 mmol of 2-thiophene methylamine (3). The mixture was sealed and stirred at 60 °C for 12 h. After the reaction was completed and the temperature was lowered to room temperature, the catalyst was filtered off, and 1,3,5-trimethoxybenzene was added as an internal standard. After rotary evaporation, deuterated chloroform was added for nuclear magnetic resonance (NMR) to confirm a yield of 98%. After purification by silica gel column chromatography, the pure product was obtained, and the NMR shift was consistent with that of the standard.

[0096] The NMR data for product P8 are as follows:

[0097] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.40 – 7.29 (m, 5H), 7.23 (dd, J =5.1, 1.3 Hz, 1H), 6.95 (dd, J = 5.1, 3.4 Hz, 1H), 6.90 (d, J = 3.4 Hz, 1H), 4.46 (s, 1H), 3.93 (s, 2H), 3.69 (s, 3H).

[0098] 13 C-NMR (126 MHz, CDCl3): δ 173.34, 143.23, 137.88, 128.90, 128.34,127.78, 126.78, 125.53, 124.90, 63.92, 52.44, 45.94.

[0099] Example 4: The reaction of carbene insertion into alkylamines to form CN bonds using a copper / coffee grounds catalyst, specifically including the following process:

[0100] ;

[0101] Under a nitrogen atmosphere, 2 mg of the copper / coffee grounds catalyst prepared in Example 1 was weighed, followed by 0.5 mL of DCE, and then 0.1 mmol of methyl diazophenylacetate (1) and 0.1 mmol of pentylamine (4). The mixture was sealed and stirred at 60 °C for 12 h. After the reaction was completed and the temperature was lowered to room temperature, the catalyst was filtered off, and 1,3,5-trimethoxybenzene was added as an internal standard. After rotary evaporation, deuterated chloroform was added for nuclear magnetic resonance (NMR) to confirm a yield of 75%. After purification by silica gel column chromatography, the pure product was obtained, and the NMR shift was consistent with that of the standard.

[0102] The NMR data for product P16 are as follows:

[0103] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.39 (d, J = 6.9 Hz, 2H), 7.34 (t, J= 7.6 Hz, 2H), 7.32 – 7.27 (m, 1H), 4.33 (s, 1H), 3.69 (s, 3H), 2.35 (d, J =11.1 Hz, 1H), 2.18 (d, J = 11.1 Hz, 1H), 0.92 (s, 9H).

[0104] 13 C-NMR (126 MHz, CDCl3): δ 173.95, 138.73, 128.68, 128.04, 127.59, 66.40, 59.97, 52.24, 31.69, 27.78.

[0105] Example 5: The reaction of carbene (ethyl diazonium acetate) catalyzing the insertion of aromatic alcohols, heterocyclic alcohols, and alkyl alcohols to form CO bonds using a copper / coffee grounds catalyst, specifically including the following process:

[0106] ;

[0107] Under a nitrogen atmosphere, 2 mg of the copper / coffee grounds catalyst prepared in Example 1 was weighed, followed by 0.5 mL of DCE, and then 0.2 mmol of ethyl diazonate (5) and 0.1 mmol of 2-(benzyloxy)ethanol (6). The mixture was sealed and stirred at 60 °C for 12 h. After the reaction was completed and the temperature was lowered to room temperature, the catalyst was filtered off, and 1,3,5-trimethoxybenzene was added as an internal standard. After evaporation to dryness, deuterated chloroform was added for nuclear magnetic resonance (NMR) to confirm a yield of 75%. After purification by silica gel column chromatography, the pure product was obtained, and the NMR shift was consistent with that of the standard.

[0108] The NMR data for product P41 are as follows:

[0109] 1H NMR (500 MHz, CDCl3) δ 7.36 – 7.29 (m, 4H), 7.29 – 7.22 (m, 1H), 4.54 (s, 2H), 4.19 (q, J = 7.2 Hz, 2H), 4.14 (s, 1H), 3.74 (dd, J = 5.7, 3.5Hz, 1H), 3.65 (dd, J = 5.7, 3.5 Hz, 1H), 1.26 (t, J = 7.2 Hz, 2H).

[0110] 13 C NMR (126 MHz, CDCl3) δ 170.61, 138.23, 128.51, 127.87, 127.76,73.41, 71.08, 69.63, 68.90, 60.94, 14.33.

[0111] Using the methods of Examples 2-4, P1-P40 were synthesized; using the method of Example 5, P41-P55 were synthesized; both yielded good results.

[0112] ;

[0113] ;

[0114] ;

[0115] .

[0116] The NMR data for product P2 are as follows:

[0117] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.42 – 7.29 (m, 5H), 7.21 (d, J =7.6 Hz, 2H), 7.13 (d, J = 7.7 Hz, 2H), 4.39 (s, 1H), 3.73 – 3.64 (m, 2H), 3.69 (s, 3H), 2.34 (s, 3H).

[0118] 13 C-NMR (126 MHz, CDCl3): δ 173.57, 138.16, 136.90, 136.46, 129.25,128.84, 128.44, 128.24, 127.74, 64.36, 52.36, 51.14, 21.24.

[0119] The NMR data for product P3 are as follows:

[0120] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.40 – 7.29 (m, 5H), 7.25 – 7.21 (m,2H), 6.89 – 6.84 (m, 2H), 4.39 (s, 1H), 3.80 (s, 3H), 3.69 (s, 3H), 3.67 (d,J = 3.3 Hz, 2H).

[0121] 13 C-NMR (126 MHz, CDCl3): δ 173.59, 158.87, 138.16, 131.62, 129.66,128.83, 128.22, 127.69, 113.91, 64.29, 55.39, 52.36, 50.82.

[0122] The NMR data for product P4 are as follows:

[0123] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.46 – 7.41 (m, 2H), 7.39 – 7.28 (m,5H), 7.22 – 7.16 (m, 2H), 4.35 (s, 1H), 3.69 (s, 3H), 3.68 (s, 2H).

[0124] 13 C-NMR (126 MHz, CDCl3): δ 173.44, 138.57, 137.91, 131.62, 130.14,128.91, 128.35, 127.64, 121.07, 64.32, 52.44, 50.71.

[0125] The NMR data for product P5 are as follows:

[0126] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.58 (d, J = 7.9 Hz, 2H), 7.45 (d, J= 7.9 Hz, 2H), 7.39 – 7.30 (m, 5H), 4.37 (s, 1H), 3.79 (s, 2H), 3.70 (s, 3H).

[0127] 13 C-NMR (126 MHz, CDCl3): δ 173.39, 143.77, 137.89, 129.58 (q, J =32.4 Hz), 128.95, 128.61, 128.42, 127.65, 125.48 (q, J = 3.7 Hz), 124.37 (q,J = 272.01 Hz), 64.49, 52.45, 50.91.

[0128] The NMR data for product P6 are as follows:

[0129] Isomer A: 1 H-NMR (500 MHz, CDCl3): δ ppm 7.36 – 7.23 (m, 10H), 4.23(s, 1H), 3.81 (q, J = 6.5 Hz, 1H), 3.71 (s, 3H), 1.39 (d, J = 6.5 Hz, 3H).

[0130] 13 C-NMR (126 MHz, CDCl3): δ174.33, 144.75, 138.34, 128.90, 128.69,128.15, 127.39, 127.34, 127.08, 62.99, 56.74, 52.30, 24.70.

[0131] Isomer B: 1 H-NMR (500 MHz, CDCl3): δ ppm 7.33 (dd, J = 11.9, 7.1Hz, 5H), 7.30 – 7.22 (m, 5H), 4.20 (s, 1H), 3.60 (s, 3H), 3.56 (d, J = 7.6Hz, 1H), 1.36 (d, J = 6.5 Hz, 3H).

[0132] 13 C-NMR (126 MHz, CDCl3): 173.37, 144.54, 138.28, 128.82, 128.67,128.23, 127.90, 127.35, 127.05, 62.71, 54.87, 52.38, 24.48.

[0133] The NMR data for product P7 are as follows:

[0134] Isomer A: 1 H-NMR (500 MHz, CDCl3): δ ppm 7.86 – 7.79 (m, 3H), 7.76 (d, J = 1.7 Hz, 1H), 7.52 (dd, J = 8.4, 1.7 Hz, 1H), 7.50 – 7.43 (m, 2H),7.36 – 7.25 (m, 5H), 4.25 (s, 1H), 3.99 (q, J = 6.5 Hz, 1H), 3.71 (s, 3H), 1.47 (d, J = 6.5 Hz, 3H).

[0135] 13 C-NMR (126 MHz, CDCl3): δ 174.38, 142.23, 138.48, 133.60, 133.13,128.91, 128.53, 128.15, 127.94, 127.81, 127.32, 126.14, 125.84, 125.76,125.18, 63.06, 56.95, 52.30, 24.73.

[0136] Isomer B: 1 H-NMR (500 MHz, CDCl3): δ ppm δ 7.83 (d, J = 8.5 Hz,2H), 7.82 – 7.78 (m, 1H), 7.63 (d, J = 1.7 Hz, 1H), 7.50 – 7.42 (m, 3H), 7.39– 7.31 (m, 3H), 7.30 – 7.27 (m, 2H), 4.22 (s, 1H), 3.73 (q, J = 6.6 Hz, 1H), 3.57 (s, 3H), 1.43 (d, J = 6.6 Hz, 3H).

[0137] 13 C-NMR (126 MHz, CDCl3): δ 173.35, 141.89, 138.29, 133.56, 133.10,128.98, 128.85, 128.56, 128.27, 127.93, 127.81, 126.14, 125.85, 125.77,125.10, 62.69, 54.91, 52.38, 24.46.

[0138] The NMR data for product P9 are as follows:

[0139] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.40 – 7.28 (m, 6H), 6.30 (dd, J =3.2, 1.8 Hz, 1H), 6.16 (d, J = 3.2 Hz, 1H), 4.40 (s, 1H), 3.73 (dd, J = 35.2,14.5 Hz, 2H), 3.67 (s, 3H).

[0140] 13 C-NMR (126 MHz, CDCl3): δ 173.19, 153.12, 142.19, 137.85, 128.85,128.32, 127.81, 110.24, 107.61, 64.24, 52.40, 43.87.

[0141] The NMR data for product P10 are as follows:

[0142] Isomer A: 1 H-NMR (500 MHz, CDCl3): δ ppm δ 7.41 – 7.37 (m, 2H),7.36 – 7.31 (m, 2H), 7.31 – 7.27 (m, 1H), 4.43 (s, 1H), 4.01 (qd, J = 7.1,4.3 Hz, 1H), 3.85 (dt, J = 8.3, 6.8 Hz, 1H), 3.74 (dt, J = 8.3, 6.8 Hz, 1H), 3.69 (s, 3H), 2.64 – 2.55 (m, 2H), 1.99 – 1.91 (m, 1H), 1.90 – 1.81 (m, 2H),1.53 (ddd, J = 11.3, 9.9, 5.7 Hz, 1H).

[0143] 13 C-NMR (126 MHz, CDCl3): δ 173.42, 138.17, 128.80, 128.21, 127.70,78.60, 68.04, 65.75, 52.34, 52.13, 29.40, 25.81.

[0144] Isomer B: 1H-NMR (500 MHz, CDCl3): δ ppm δ 7.40 – 7.36 (m, 2H),7.36 – 7.31 (m, 2H), 7.31 – 7.27 (m, 1H), 4.44 (s, 1H), 4.02 (qd, J = 7.1,3.9 Hz, 1H), 3.82 (dt, J = 8.2, 6.7 Hz, 1H), 3.73 (dt, J = 8.2, 6.7 Hz, 1H), 3.68 (s, 3H), 2.67 (dd, J = 11.9, 4.0 Hz, 1H), 2.53 (dd, J = 11.9, 7.3 Hz,1H), 1.97 – 1.90 (m, 1H), 1.85 (ttd, J = 8.2, 6.8, 2.1 Hz, 2H), 1.60 – 1.51(m, 1H).

[0145] 13 C-NMR (126 MHz, CDCl3): δ 173.30, 138.11, 128.82, 128.24, 127.69,78.31, 68.12, 65.70, 52.36, 51.76, 29.28, 25.88.

[0146] The NMR data for product P11 are as follows:

[0147] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.38 – 7.27 (m, 5H), 5.47 (dt, J =3.9, 2.3 Hz, 1H), 4.39 (s, 1H), 3.69 (s, 3H), 2.64 (dt, J = 11.0, 7.0 Hz,1H), 2.56 (dt, J = 11.0, 7.0 Hz, 1H), 2.16 (t, J = 7.0 Hz, 2H), 2.02 – 1.95(m, 2H), 1.93 – 1.77 (m, 2H), 1.66 – 1.50 (m, 4H).

[0148] 13C-NMR (126 MHz, CDCl3): δ 173.62, 138.34, 135.29, 128.85, 128.23,127.56, 123.11, 65.64, 52.34, 45.58, 38.38, 28.21, 25.39, 23.07, 22.59.

[0149] The NMR data for product P12 are as follows:

[0150] Isomer A: 1 H-NMR (500 MHz, CDCl3): δ ppm 7.45 – 7.39 (m, 3H), 7.36– 7.31 (m, 2H), 7.31 – 7.26 (m, 1H), 7.17 (tt, J = 7.3, 5.4 Hz, 2H), 7.08(dd, J = 6.6, 2.2 Hz, 1H), 4.59 (s, 1H), 3.78 (t, J = 4.2 Hz, 1H), 3.75 (s,3H), 2.82 (dt, J = 16.8, 5.0 Hz, 1H), 2.71 (ddd, J = 16.5, 10.0, 5.8 Hz, 1H),2.11 – 2.01 (m, 1H), 1.90 (ddt, J = 13.3, 6.7, 3.5 Hz, 1H), 1.80 – 1.74 (m,1H), 1.70 (ddq, J = 13.3, 7.4, 3.5 Hz, 1H).

[0151] 13 C-NMR (126 MHz, CDCl3): δ 174.55, 138.81, 138.57, 137.73, 129.29,129.23, 128.78, 128.05, 127.52, 127.13, 126.03, 63.34, 53.95, 52.37, 29.38,28.34, 18.36.

[0152] Isomer B: 1H-NMR (500 MHz, CDCl3): δ ppm 7.52 – 7.47 (m, 2H), 7.42– 7.36 (m, 2H), 7.35 – 7.30 (m, 1H), 7.28 (dd, J = 5.5, 3.6 Hz, 1H), 7.14(dd, J = 5.7, 3.4 Hz, 2H), 7.06 (dd, J = 5.5, 3.6 Hz, 1H), 4.60 (s, 1H), 3.69(s, 3H), 3.63 (t, J = 5.0 Hz, 1H), 2.82 (dt, J = 16.7, 5.7 Hz, 1H), 2.69(ddd, J = 16.7, 8.6, 5.8 Hz, 1H), 2.07 – 1.96 (m, 1H), 1.87 – 1.75 (m, 2H), 1.69 (tdd, J = 9.8, 8.1, 4.7 Hz, 1H).

[0153] 13 C-NMR (126 MHz, CDCl3): δ 173.70, 138.86, 138.71, 137.71, 129.11,128.95, 128.83, 128.23, 127.98, 126.93, 125.89, 62.90, 52.53, 52.49, 29.41,28.06, 19.01.

[0154] The NMR data for product P13 are as follows:

[0155] Isomer A: 11H-NMR (500 MHz, CDCl3): δ ppm 7.51 – 7.47 (m, 2H), 7.39 (dd, J = 8.3, 6.7 Hz, 2H), 7.35 – 7.30 (m, 1H), 7.28 (dd, J = 5.6, 3.7 Hz, 1H), 7.14 (dd, J = 5.8, 3.4 Hz, 2H), 7.06 (dd, J = 5.5, 3.6 Hz, 1H), 4.61 (s, 1H), 3.69 (s, 3H), 3.63 (t, J = 5.0 Hz, 1H), 2.82 (dt, J = 16.7, 5.7 Hz, 1H), 2.69 (ddd, J = 16.6, 8.6, 5.8 Hz, 1H), 2.07 – 1.96 (m, 1H), 1.86 – 1.75 (m, 2H), 1.73 – 1.64 (m, 1H).

[0156] 13 13C-NMR (126 MHz, CDCl3): δ 173.67, 138.75, 138.70, 137.73, 129.12, 128.95, 128.85, 128.26, 127.99, 126.95, 125.90, 62.89, 52.56, 52.51, 29.41, 28.04, 19.03.

[0157] Isomer B: 1 1H-NMR (500 MHz, CDCl3): δ ppm 7.44 – 7.39 (m, 3H), 7.36 – 7.31 (m, 2H), 7.29 (d, J = 7.1 Hz, 1H), 7.17 (qd, J = 7.4, 3.7 Hz, 2H), 7.11 – 7.06 (m, 1H), 4.60 (s, 1H), 3.85 – 3.76 (m, 1H), 3.74 (s, 3H), 2.82 (dt, J = 16.8, 5.1 Hz, 1H), 2.71 (ddd, J = 16.5, 10.0, 5.8 Hz, 1H), 2.11 – 2.01 (m, 1H), 1.96 – 1.85 (m, 1H), 1.81 – 1.64 (m, 2H).

[0158] 13C-NMR (126 MHz, CDCl3): 174.56, 138.80, 138.56, 137.74, 129.29,129.23, 128.78, 128.05, 127.52, 127.13, 126.03, 63.34, 53.95, 52.37, 29.38,28.34, 18.36.

[0159] The NMR data for product P14 are as follows:

[0160] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.38 – 7.27 (m, 5H), 4.48 (s, 1H), 3.68 (s, 3H), 2.72 (p, J = 6.2 Hz, 1H), 2.01 (s, 1H), 1.06 (t, J = 5.7 Hz,6H).

[0161] 13 C-NMR (126 MHz, CDCl3): δ 174.05, 138.56, 128.85, 128.12, 127.45,63.01, 52.33, 46.32, 23.08, 22.76

[0162] The NMR data for product P15 are as follows:

[0163] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.41 – 7.28 (m, 5H), 4.39 (s, 1H), 3.70 (s, 3H), 2.55 (dt, J = 11.1, 7.3 Hz, 1H), 2.48 (dt, J = 11.1, 7.3 Hz,1H), 1.54 (h, J = 7.4 Hz, 2H), 0.91 (t, J = 7.4 Hz, 3H).

[0164] 13 C-NMR (126 MHz, CDCl3): δ 173.61, 138.13, 128.87, 128.27, 127.61,65.60, 52.39, 49.77, 23.20, 11.85.

[0165] The NMR data for product P17 are as follows:

[0166] 1H-NMR (500 MHz, CDCl3): δ ppm 7.44 – 7.39 (m, 2H), 7.36 – 7.28 (m,3H), 4.19 (s, 1H), 3.70 (s, 3H), 2.44 (dt, J = 14.9, 7.7 Hz, 1H), 2.34 (td, J= 10.8, 6.9 Hz, 1H), 2.25 (s, 3H), 1.52 – 1.41 (m, 2H), 1.30 – 1.21 (m, 2H), 0.85 (t, J = 7.4 Hz, 3H).

[0167] 13 C-NMR (126 MHz, CDCl3): δ 172.64, 136.79, 128.97, 128.58, 128.27,73.25, 54.68, 51.95, 39.37, 29.19, 20.57, 14.12.

[0168] The NMR data for product P18 are as follows:

[0169] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.39 – 7.32 (m, 4H), 7.32 – 7.27 (m,1H), 4.36 (s, 1H), 3.69 (s, 3H), 3.44 (t, J = 6.3 Hz, 2H), 3.31 (s, 3H), 2.67(dt, J = 11.4, 6.9 Hz, 1H), 2.58 (dt, J = 11.3, 7.0 Hz, 1H), 1.77 (p, J = 6.6Hz, 2H).

[0170] 13 C-NMR (126 MHz, CDCl3): δ173.66, 138.36, 128.84, 128.21, 127.57,71.27, 65.79, 58.76, 52.35, 45.30, 30.15.

[0171] The NMR data for product P19 are as follows:

[0172] 1H-NMR (500 MHz, CDCl3): δ ppm 7.54 – 7.48 (m, 2H), 7.34 (t, J =7.3 Hz, 2H), 7.31 – 7.27 (m, 1H), 7.25 – 7.20 (m, 2H), 6.81 (t, J = 7.3 Hz,1H), 6.74 (d, J = 8.1 Hz, 3H), 5.30 (s, 1H), 3.69 (dt, J = 11.3, 4.3 Hz, 1H), 3.60 (ddd, J = 11.4, 7.6, 5.7 Hz, 1H), 3.56 – 3.46 (m, 2H).

[0173] 13 C-NMR (126 MHz, CDCl3): δ 170.64, 148.13, 137.82, 129.49, 128.86,128.02, 126.90, 118.87, 113.80, 65.38, 43.79, 39.33.

[0174] The NMR data for product P20 are as follows:

[0175] Isomer A: 1 H-NMR (500 MHz, CDCl3): δ ppm δ 7.40 (d, J = 8.6 Hz, 2H), 7.37 – 7.19 (m, 10H), 6.80 (d, J = 8.4 Hz, 2H), 5.20 (dd, J = 8.9, 4.2Hz, 1H), 4.26 (s, 1H), 3.62 (s, 3H), 2.74 – 2.57 (m, 2H), 2.30 (s, 3H), 2.19 – 2.08 (m, 1H), 2.01 – 1.91 (m, 1H).

[0176] 13C-NMR (126 MHz, CDCl3): δ 172.40, 160.72, 141.43, 136.42, 128.87,128.57, 128.29, 127.86, 126.74 (q, J = 3.9 Hz), 125.88, 124.50 (q, J = 270.9Hz), 122.70 (q, J = 32.5 Hz), 115.88, 78.01, 72.85, 51.83, 50.40, 39.40,36.66.

[0177] Isomer B: 1 H-NMR (500 MHz, CDCl3): δ ppm δ 7.42 (d, J = 8.5 Hz, 2H), 7.34 – 7.15 (m, 10H), 6.82 (d, J = 8.5 Hz, 2H), 5.28 (dd, J = 9.0, 4.1Hz, 1H), 4.17 (s, 1H), 3.66 (s, 3H), 2.79 – 2.66 (m, 1H), 2.54 – 2.41 (m,1H), 2.30 (s, 3H), 2.15 – 2.05 (s, 1H), 2.03 – 1.91 (s, 1H).

[0178] 13 C-NMR (126 MHz, CDCl3): δ 172.38, 160.78, 141.43, 136.47, 128.95,128.86, 128.58, 128.34, 127.86, 126.80 (q, J = 4.0 Hz), 125.89, 124.56 (q, J = 270.8 Hz), 122.76 (q, J = 32.8 Hz), 115.84, 77.78, 73.23, 51.95, 50.75, 39.11, 36.53.

[0179] The NMR data for product P21 are as follows:

[0180] Isomer A: 11H-NMR (500 MHz, CDCl3): δ ppm 8.19 (dd, J = 8.0, 1.6 Hz, 1H), 7.76 (dd, J = 7.7, 1.6 Hz, 1H), 7.45 (dddd, J = 14.7, 8.2, 6.8, 1.5 Hz, 2H), 7.39 – 7.31 (m, 3H), 7.28 – 7.23 (m, 1H), 7.23 – 7.13 (m, 4H), 6.98 (d, J = 3.5 Hz, 1H), 6.90 (dd, J = 5.0, 3.5 Hz, 1H), 6.80 (d, J = 7.7 Hz, 1H), 5.69 (dd, J = 7.9, 4.9 Hz, 1H) 4.25 (s, 1H), 3.57 (s, 3H), 2.72 (tq, J = 13.0, 7.1 Hz, 2H), 2.43 (dq, J = 13.6, 7.0 Hz, 1H), 2.32 (s, 3H), 2.20 (dq, J = 13.6, 7.0 Hz, 1H).

[0181] 13 13C-NMR (126 MHz, CDCl3): δ 172.44, 153.50, 145.56, 136.41, 134.68, 128.83, 128.55, 128.20, 127.51, 126.64, 126.36, 126.24, 125.81, 125.26, 124.74, 124.62, 122.30, 120.55, 106.97, 74.22, 73.05, 51.85, 50.76, 39.40, 36.93.

[0182] Isomer B 1H-NMR (500 MHz, CDCl3): δ ppm 8.15 (d, J = 8.3 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.49 – 7.36 (m, 3H), 7.31 – 7.23 (m, 3H), 7.18 (d,J = 5.0 Hz, 1H), 7.15 – 7.08 (m, 3H), 6.97 (d, J = 3.5 Hz, 1H), 6.90 (dd, J =5.0, 3.5 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), 5.74 (dd, J = 8.1, 4.8 Hz, 1H), 4.17 (s, 1H), 3.64 (s, 3H), 2.80 (dt, J = 13.9, 7.3 Hz, 1H), 2.62 (dq, J =13.7, 6.9 Hz, 1H), 2.38 (dt, J = 13.9, 6.9 Hz, 1H), 2.33 (s, 3H), 2.22 (dq, J= 13.1, 6.5 Hz, 1H).

[0183] 13 C-NMR (126 MHz, CDCl3): δ 172.46, 153.54, 145.63, 136.46, 134.69,128.87, 128.52, 128.18, 127.51, 126.63, 126.36, 126.23, 125.84, 125.24,124.72, 124.65, 122.30, 120.54, 106.83, 74.04, 73.23, 51.93, 50.85, 39.33,36.83.

[0184] The NMR data for product P22 are as follows:

[0185] 1H-NMR (500 MHz, CDCl3): δ ppm 7.54 – 7.45 (m, 2H), 7.41 – 7.30 (m,4H), 7.15 – 7.10 (m, 1H), 7.09 – 7.04 (m, 2H), 7.03 – 6.98 (m, 1H), 6.85(ddd, J = 8.4, 5.4, 3.3 Hz, 1H), 6.52 – 6.45 (m, 1H), 4.08 (s, 1H), 3.71 (s,3H), 3.24 – 3.03 (m, 4H), 2.86 – 2.45 (m, 4H), 2.35 (s, 3H), 2.29 (s, 3H).

[0186] 13 C-NMR (126 MHz, CDCl3): δ 172.21, 149.18, 142.60, 139.33, 136.38,135.97, 134.74, 131.79, 129.10, 128.82, 128.62, 128.06, 127.92, 126.18,125.59, 124.49, 119.98, 74.64, 52.28, 51.88, 51.49, 21.32, 20.70.

[0187] The NMR data for product P23 are as follows:

[0188] 1 H-NMR (500 MHz, CDCl3): δ ppm 8.28 (d, J = 4.7 Hz, 2H), 7.48 –7.43 (m, 2H), 7.39 – 7.31 (m, 3H), 6.46 (t, J = 4.7 Hz, 1H), 4.05 (s, 1H), 3.84 (t, J = 5.1 Hz, 4H), 3.70 (s, 3H), 2.52 (dq, J = 5.7, 3.0 Hz, 4H).

[0189] 13 C-NMR (126 MHz, CDCl3): δ 172.00, 161.71, 157.83, 135.61, 129.00,128.83, 128.66, 109.97, 77.16, 74.23, 52.24, 51.10, 43.65.

[0190] The NMR data for product P24 are as follows:

[0191] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.49 (dd, J = 7.6, 1.8 Hz, 1H), 7.44(d, J = 7.5 Hz, 2H), 7.40 – 7.21 (m, 7H), 7.16 (td, J = 7.7, 1.6 Hz, 1H),7.05 (d, J = 7.5 Hz, 1H), 6.87 (td, J = 7.5, 1.5 Hz, 1H), 4.08 (d, J = 14.9Hz, 1H), 3.85 – 3.04 (m, 4H), 3.69 (s, 3H), 2.78 – 2.30 (m, 4H).

[0192] 13 C-NMR (126 MHz, CDCl3): δ 171.95, 160.80, 160.78, 149.05, 140.10,140.08, 135.65, 135.62, 134.18, 132.31, 132.26, 130.86, 129.22, 129.11,128.98, 128.95, 128.79, 128.65, 128.63, 128.33, 128.10, 125.43, 122.91,74.21, 74.05, 52.22, 52.17, 50.94.

[0193] The NMR data for product P25 are as follows:

[0194] 1 H-NMR (500 MHz, CDCl3): δ ppm 7.42 – 7.38 (m, 2H), 7.36 – 7.11 (m,12H), 4.21 (s, 1H), 4.00 (s, 1H), 3.66 (d, J = 2.2 Hz, 3H), 2.77 – 2.16 (m,8H).

[0195] 13C-NMR (126 MHz, CDCl3): δ 172.10, 142.18, 142.14, 141.38, 135.79,132.65, 129.34, 128.97, 128.75, 128.69, 128.51, 128.00, 127.27, 75.39, 74.36,52.16, 51.66, 51.48.

[0196] The NMR data for product P26 are as follows:

[0197] Isomer A: 1 H-NMR (500 MHz, CDCl3): δ ppm δ 7.32 – 7.14 (m, 4H), 7.00 – 6.90 (m, 2H), 6.51 (dd, J = 9.1, 1.4 Hz, 1H), 5.84 (dd, J = 6.8, 1.4Hz, 1H), 4.25 (s, 1H), 4.15 (d, J = 15.3 Hz, 1H), 3.94 – 3.84 (m, 1H), 3.68(s, 3H), 3.01 – 2.59 (m, 5H), 2.44 (dd, J = 12.9, 3.9 Hz, 1H), 1.99 – 1.77(m, 2H).

[0198] Isomer B: 1 H-NMR (500 MHz, CDCl3): δ ppm 7.32 – 7.14 (m, 4H), 7.07– 7.01 (m, 2H), 6.51 (dd, J = 9.1, 1.4 Hz, 1H), 5.89 (dd, J = 6.9, 1.4 Hz, 1H), 4.10 (s, 1H), 4.03 (d, J = 15.3 Hz, 1H), 3.94 – 3.84 (m, 1H), 3.65 (s,3H), 3.01 – 2.59 (m, 4H), 2.44 (dd, J = 12.9, 3.9 Hz, 2H), 1.99 – 1.77 (m,2H).

[0199] The NMR data for product P27 are as follows:

[0200] Isomer A: 11H-NMR (500 MHz, CDCl3): δ ppm 7.45 (d, J = 6.6 Hz, 2H), 7.40 – 7.29 (m, 3H), 7.15 (dd, J = 8.4, 5.4 Hz, 2H), 6.96 (t, J = 8.7 Hz, 2H), 6.58 (d, J = 8.5 Hz, 1H), 6.23 (d, J = 2.4 Hz, 1H), 6.03 (dd, J = 8.5, 2.5 Hz, 1H), 5.86 (s, 2H), 4.15 (s, 1H), 3.71 (s, 3H), 3.48 (dd, J = 9.5, 2.8 Hz, 1H), 3.37 (dd, J = 9.5, 6.7 Hz, 1H), 3.07 (t, J = 11.9 Hz, 2H), 2.51 (td, J = 11.9, 4.0 Hz, 1H), 2.32 (td, J = 11.8, 2.6 Hz, 1H), 2.25 – 2.12 (m, 1H), 2.03 (t, J = 11.0 Hz, 1H), 1.94 (qd, J = 12.5, 3.8 Hz, 1H), 1.81 (d, J = 12.9 Hz, 1H).

[0201] 13 13C-NMR (126 MHz, CDCl3): δ 172.33, 162.62, 160.68, 154.34, 148.22, 141.68, 139.76, 136.06, 129.02, 128.91, 128.75, 128.48, 115.59, 115.42, 107.92, 105.77, 101.20, 98.19, 74.29, 69.53, 55.05, 52.14, 51.99, 44.13, 42.27, 34.31.

[0202] Isomer B 1H-NMR (500 MHz, CDCl3): δ ppm 7.46 (d, J = 7.2 Hz, 2H), 7.40 – 7.29 (m, 3H), 7.15 (dd, J = 8.4, 5.4 Hz, 2H), 6.96 (t, J = 8.7 Hz, 2H), 6.62 (d, J = 8.4 Hz, 1H), 6.31 (d, J = 2.4 Hz, 1H), 6.10 (dd, J = 8.5,2.5 Hz, 1H), 5.88 (s, 2H), 4.10 (s, 1H), 3.71 (s, 3H), 3.56 (dd, J = 9.6, 2.4Hz, 1H), 3.44 (dd, J = 9.5, 5.5 Hz, 1H), 3.27 (d, J = 7.9 Hz, 1H), 2.88 (d, J= 11.0 Hz, 1H), 2.50 (dt, J = 11.6, 5.5 Hz, 1H), 2.29 (t, J = 8.3 Hz, 2H), 2.04 – 1.93 (m, 1H), 1.87 (qd, J = 12.3, 3.6 Hz, 1H), 1.79 – 1.67 (m, 1H).

[0203] 13 C-NMR (126 MHz, CDCl3): δ 172.33, 162.63, 160.68, 154.49, 148.27,141.69, 139.76, 135.98, 129.02, 128.98, 128.76, 128.53, 115.60, 115.44,107.97, 105.68, 101.22, 98.13, 74.57, 69.47, 55.94, 52.22, 51.63, 44.07,42.26, 34.19.

[0204] The NMR data for product P28 are as follows:

[0205] 1H-NMR (500 MHz, CDCl3): δ ppm 8.36 (ddd, J = 5.1, 3.7, 1.7 Hz,1H), 7.45 – 7.38 (m, 3H), 7.31 (q, J = 7.1 Hz, 3H), 7.12 (dt, J = 3.5, 1.6Hz, 1H), 7.11 – 7.08 (m, 2H), 7.06 (dt, J = 7.7, 5.0 Hz, 1H)4.05 (d, J = 12.8Hz, 1H), 3.67 (d, J = 1.6 Hz, 3H), 3.44 – 3.28 (m, 2H), 2.87 – 2.63 (m, 4H),2.55 (ddt, J = 13.8, 9.1, 5.1 Hz, 1H), 2.49 – 2.40 (m, 1H), 2.39 – 2.24 (m,3H), 2.24 – 2.07 (m, 1H).

[0206] 13 C-NMR (126 MHz, CDCl3): δ 172.23, 157.65, 146.71, 139.63, 138.92,137.82, 137.37, 136.09, 133.55, 132.78, 130.98, 129.07, 128.86, 128.67,128.46, 126.13, 126.10, 122.20, 52.91, 52.80, 52.72, 52.11, 31.96, 31.56,30.94, 30.70.

[0207] The NMR data for product P29 are as follows:

[0208] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.32 (d, J = 4.4 Hz, 4H), 7.27 (d, J= 7.7 Hz, 3H), 7.17 (d, J = 7.8 Hz, 2H), 4.37 (s, 1H), 3.72 (dd, J = 18.9,13.2 Hz, 1H), 3.68 (s, 3H), 2.35 (s, 3H).

[0209] 13C-NMR (126 MHz, CDCl3) δ 173.64, 139.57, 138.04, 135.08, 129.56,128.55, 128.47, 127.62, 127.27, 64.13, 52.34, 51.35, 21.29.

[0210] The NMR data for product P30 are as follows:

[0211] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.36 – 7.23 (m, 7H), 6.93 – 6.86 (m,2H), 4.35 (s, 1H), 3.81 (s, 3H), 3.72 (dd, J = 19.6, 13.3 Hz, 2H), 3.69 (s,3H).

[0212] 13 C-NMR (126 MHz, CDCl3) δ 173.71, 159.59, 139.57, 130.16, 128.87,128.56, 128.47, 127.27, 114.24, 63.77, 55.40, 52.32, 51.33.

[0213] The NMR data for product P31 are as follows:

[0214] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.36 – 7.17 (m, 7H), 6.99 (t, J = 8.7Hz, 2H), 4.32 (s, 1H), 3.66 (dd, J = 17.6, 5.8 Hz, 2H), 3.64 (s, 3H).

[0215] 13 C NMR (126 MHz, CDCl3) δ 173.38, 163.65, 161.69, 139.42, 133.95, 133.92, 129.42, 129.35, 128.60, 128.41, 127.35, 115.81, 115.63, 63.69, 52.44,51.43.

[0216] The NMR data for product P32 are as follows:

[0217] 1H-NMR (500 MHz, CDCl3) δ ppm 7.36 – 7.23 (m, 6H), 7.19 – 7.10 (m,2H), 7.04 – 6.97 (m, 1H), 4.39 (s, 1H), 3.72 (dd, J = 19.3, 13.2 Hz, 2H),3.70 (s, 3H).

[0218] The NMR data for product P33 are as follows:

[0219] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.62 (d, J = 8.1 Hz, 2H), 7.53 (d, J= 8.1 Hz, 2H), 7.38 – 7.22 (m, 5H), 4.45 (s, 1H), 3.73 (dd, J = 22.1, 13.2Hz, 2H), 3.70 (s, 3H).

[0220] The NMR data for product P34 are as follows:

[0221] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.37 – 7.24 (m, 9H), 4.37 (s, 1H), 3.72 (dd, J = 30.7, 13.3 Hz, 2H), 3.69 (s, 3H).

[0222] 13 C NMR (126 MHz, CDCl3) δ 173.02, 139.12, 136.45, 134.18, 129.19,129.04, 128.65, 128.48, 127.46, 63.66, 52.56, 51.34.

[0223] The NMR data for product P35 are as follows:

[0224] 1H-NMR (500 MHz, CDCl3) δ ppm 8.11 – 8.04 (m, 1H), 7.87 (dd, J =6.2, 3.3 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.55 – 7.43 (m, 4H), 7.33 (d, J =4.3 Hz, 4H), 7.30 – 7.25 (m, 1H), 5.11 (s, 1H), 3.83 (s, 2H), 3.68 (s, 3H).

[0225] 13 C NMR (126 MHz, CDCl3) δ 173.83, 139.32, 134.24, 133.95, 131.65,129.05, 128.94, 128.71, 128.59, 127.41, 126.55, 125.95, 125.68, 125.46,123.77, 61.19, 52.49, 51.76.

[0226] The NMR data for product P36 are as follows:

[0227] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.89 – 7.81 (m, 4H), 7.55 – 7.46 (m,3H), 7.34 (d, J = 4.3 Hz, 4H), 7.30 – 7.24 (m, 1H), 4.58 (s, 1H), 3.78 (q, J= 13.2 Hz, 2H), 3.70 (s, 3H).

[0228] 13 C NMR (126 MHz, CDCl3) δ 173.41, 139.46, 135.43, 133.44, 133.32,128.73, 128.60, 128.50, 128.14, 127.83, 127.34, 127.05, 126.43, 126.33,125.36, 64.50, 52.46, 51.37

[0229] The NMR data for product P37 are as follows:

[0230] 1H-NMR (500 MHz, CDCl3) δ ppm 7.35 – 7.29 (m, 5H), 7.29 – 7.23 (m,2H), 7.11 (d, J = 4.8 Hz, 1H), 4.51 (s, 1H), 3.77 (s, 2H), 3.73 (s, 3H).

[0231] 13 C NMR (126 MHz, CDCl3) δ 173.28, 139.39, 138.76, 128.59, 128.48,127.35, 126.69, 126.34, 123.03, 60.35, 52.42, 51.58.

[0232] The NMR data for product P38 are as follows:

[0233] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.42 – 7.38 (m, 2H), 7.37 – 7.33 (m,2H), 7.34 – 7.23 (m, 6H), 4.38 (s, 1H), 4.23 – 4.08 (m, 2H), 3.74 (s, 2H),1.21 (t, J = 7.1 Hz, 3H).

[0234] 13 C NMR (126 MHz, CDCl3) δ 13C NMR (126 MHz, CDCl3) δ 173.11, 139.66,138.31, 128.79, 128.56, 128.48, 128.15, 127.66, 127.26, 64.58, 61.29, 51.51,14.25.

[0235] The NMR data for product P39 are as follows:

[0236] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.39 (d, J = 7.0 Hz, 2H), 7.37 – 7.28 (m, 10H), 7.28 – 7.23 (m, 1H), 7.23 – 7.18 (m, 2H), 5.14 (dd, J = 33.3, 12.5Hz, 2H), 4.46 (s, 1H), 3.75 (s, 2H).

[0237] 13 C NMR (126 MHz, CDCl3) δ 172.90, 139.47, 137.98, 135.73, 128.82,128.61, 128.56, 128.50, 128.33, 128.25, 128.07, 127.73, 127.30, 66.88, 64.55,51.47.

[0238] The NMR data for product P40 are as follows:

[0239] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.42 – 7.38 (m, 2H), 7.38 – 7.34 (m,2H), 7.34 – 7.29 (m, 5H), 7.29 – 7.23 (m, 1H), 5.83 (ddt, J = 16.4, 10.9, 5.6Hz, 1H), 5.24 – 5.11 (m, 2H), 4.65 – 4.54 (m, 2H), 4.43 (s, 1H), 3.68 (dd, J= 19.4, 16.3, Hz, 2H).

[0240] 13 C NMR (126 MHz, CDCl3) δ 172.65, 137.91, 131.84, 128.85, 128.59,128.54, 128.30, 127.76, 127.35, 118.45, 65.76, 64.47, 51.42, 29.84.

[0241] The NMR data for product P42 are as follows:

[0242] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.89 – 7.79 (m, 3H), 7.75 (s, 1H), 7.49 (td, J = 6.4, 3.2 Hz, 3H), 4.74 (q, J = 6.5 Hz, 1H), 4.18 (q, J = 7.1Hz, 2H), 3.96 (dd, J = 53.9, 16.4 Hz, 2H), 1.61 (d, J = 6.5 Hz, 3H), 1.24 (t,J = 7.1 Hz, 3H).

[0243] 13 C NMR (126 MHz, CDCl3) δ 170.70, 139.94, 133.35, 133.33, 128.74,128.01, 127.87, 126.37, 126.12, 125.72, 124.30, 78.80, 66.03, 60.91, 23.91,14.31.

[0244] The NMR data for product P43 are as follows:

[0245] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.38 (d, J = 7.1 Hz, 4H), 7.33 (dd, J= 8.6, 6.7 Hz, 4H), 7.30 – 7.24 (m, 3H), 5.58 (s, 1H), 4.22 (q, J = 7.1 Hz,2H), 4.10 (s, 2H), 1.28 (t, J = 7.2 Hz, 3H).

[0246] 13 C NMR (126 MHz, CDCl3) δ 170.60, 141.13, 128.60, 127.92, 127.48, 83.69, 66.04, 60.98, 14.34.

[0247] The NMR data for product P44 are as follows:

[0248] 1 H-NMR (500 MHz, CDCl3) δ ppm 4.74 (t, J = 1.9 Hz, 2H), 4.24 (q, J= 7.2 Hz, 2H), 4.13 (s, 2H), 1.30 (t, J = 7.2 Hz, 3H).

[0249] The NMR data for product P45 are as follows:

[0250] 1H-NMR (500 MHz, CDCl3) δ ppm 7.58 – 7.50 (m, 1H), 7.23 – 7.15 (m,2H), 7.14 – 7.06 (m, 1H), 4.58 (t, J = 4.8 Hz, 1H), 4.24 (q, J = 7.2 Hz, 2H), 4.18 (s, 2H), 2.84 (dt, J = 17.0, 5.8 Hz, 1H), 2.72 (ddd, J = 16.9, 8.4, 5.7Hz, 1H), 2.03 (dqt, J = 17.0, 5.9, 3.1 Hz, 2H), 1.91 (tp, J = 10.0, 3.2 Hz, 1H), 1.75 (dtt, J = 12.4, 6.5, 3.3 Hz, 1H), 1.31 (t, J = 7.1 Hz, 3H).

[0251] 13 C NMR (126 MHz, CDCl3) δ 171.15, 137.87, 135.81, 129.76, 129.08,127.94, 125.96, 75.99, 65.59, 60.98, 29.18, 27.87, 18.84, 14.38.

[0252] The NMR data for product P46 are as follows:

[0253] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.46 (d, J = 7.3 Hz, 1H), 7.32 – 7.18(m, 3H), 5.07 (dd, J = 6.6, 3.7 Hz, 1H), 4.23 (q, J = 7.1 Hz, 2H), 4.15 (d, J= 1.4 Hz, 2H), 3.11 (ddd, J = 15.1, 8.2, 6.4 Hz, 1H), 2.82 (ddd, J = 16.0,8.5, 4.8 Hz, 1H), 2.35 (ddt, J = 13.2, 8.4, 6.5 Hz, 1H), 2.16 (dddd, J =13.3, 8.4, 4.8, 3.7 Hz, 1H), 1.29 (t, J = 7.1 Hz, 3H).

[0254] 13C NMR (126 MHz, CDCl3) δ 170.89, 144.46, 141.84, 128.86, 126.53, 125.48, 125.11, 83.93, 65.91, 61.02, 32.27, 30.33, 14.37.

[0255] The NMR data for product P47 are as follows:

[0256] 1 H-NMR (500 MHz, CDCl3) δ ppm 7.32 (dd, J = 5.0, 1.2 Hz, 1H), 7.04 (d, J = 3.5 Hz, 1H), 6.98 (dd, J = 5.1, 3.5 Hz, 1H), 4.81 (s, 2H), 4.23 (q, J= 7.2 Hz, 2H), 4.09 (s, 2H), 1.29 (t, J = 7.2 Hz, 3H).

[0257] 13 C NMR (126 MHz, CDCl3) δ 170.37, 139.63, 127.58, 126.89, 126.69, 67.55, 66.70, 61.11, 14.35.

[0258] The NMR data for product P48 are as follows:

[0259] 1 H-NMR (500 MHz, CDCl3) δ ppm 5.35 (dt, J = 5.5, 2.1 Hz, 1H), 4.21(q, J = 7.2 Hz, 2H), 4.11 (s, 2H), 3.24 (tt, J = 11.4, 4.5 Hz, 1H), 2.38(ddd, J = 13.2, 4.8, 2.4 Hz, 1H), 2.27 (ddq, J = 14.9, 11.5, 2.8 Hz, 1H), 2.07 – 1.75 (m, 5H), 1.59 – 0.81 (m, 36H), 0.67 (s, 3H).

[0260] 13C NMR (126 MHz, CDCl3) δ 171.06, 140.67, 122.08, 80.17, 65.91,60.96, 56.90, 56.29, 50.30, 42.46, 39.91, 39.66, 38.84, 37.27, 36.96, 36.33,35.92, 32.08, 32.01, 28.37, 28.22, 28.16, 24.43, 23.96, 22.96, 22.70, 21.21,19.49, 18.86, 14.35, 12.00.

[0261] The NMR data for product P49 are as follows:

[0262] 1 H-NMR (500 MHz, CDCl3) δ ppm 4.21 (q, J = 7.2 Hz, 2H), 4.10 (q, J= 16.1 Hz, 2H), 3.15 (td, J = 10.6, 4.1 Hz, 1H), 2.30 (heptd, J = 7.0, 2.7Hz, 1H), 2.06 (dtd, J = 12.1, 3.7, 1.8 Hz, 1H), 1.64 (tp, J = 9.9, 3.1 Hz, 2H), 1.38 – 1.21 (m, 5H), 1.02 – 0.74 (m, 12H).

[0263] The NMR data for product P50 are as follows:

[0264] 1 H-NMR (500 MHz, CDCl3) δ ppm 4.20 (q, J = 7.1 Hz, 2H), 4.07 (s,2H), 2.20 – 2.11 (m, 3H), 1.77 (d, J = 2.9 Hz, 6H), 1.68 – 1.53 (m, 6H), 1.28(t, J = 7.1 Hz, 3H).

[0265] 13 C NMR (126 MHz, CDCl3) δ 171.78, 73.96, 60.88, 59.29, 41.30, 36.42,30.65, 14.36.

[0266] The NMR data for product P51 are as follows:

[0267] 1 H-NMR (500 MHz, CDCl3) δ ppm 4.21 (q, J = 7.2 Hz, 2H), 4.18 – 3.99 (m, 3H), 3.45 (tt, J = 19.8, 10.3 Hz, 4H), 2.12 – 1.85 (m, 2H), 1.45 (s, 9H),1.28 (t, J = 7.1 Hz, 3H).

[0268] 13 C NMR (126 MHz, CDCl3) 170.38, 154.73, 154.61, 79.43, 78.60, 66.48,61.14, 51.50, 50.72, 44.11, 43.65, 31.61, 30.47, 28.63, 14.31.

[0269] The NMR data for product P52 are as follows:

[0270] 1 H-NMR (500 MHz, CDCl3) δ ppm 4.21 (q, J = 7.1 Hz, 2H), 4.05 (s,2H), 3.32 (d, J = 6.6 Hz, 2H), 1.82 – 1.61 (m, 6H), 1.28 (t, J = 7.1 Hz, 3H),1.26 – 1.09 (m, 3H), 0.94 (qd, J = 12.1, 3.2 Hz, 2H).

[0271] The NMR data for product P53 are as follows:

[0272] 1H-NMR (500 MHz, CDCl3) δ ppm 4.20 (q, J = 7.1 Hz, 2H), 4.15 (dd, J= 27.0, 16.4 Hz, 2H), 4.09 (qd, J = 6.6, 3.9 Hz, 1H), 3.87 (dt, J = 8.3, 6.6Hz, 1H), 3.80 – 3.72 (m, 1H), 3.62 (dd, J = 10.1, 3.9 Hz, 1H), 3.52 (dd, J =10.2, 6.2 Hz, 1H), 2.02 – 1.80 (m, 3H), 1.70 – 1.60 (m, 1H), 1.27 (t, J = 7.1Hz, 3H).

[0273] 13 C NMR (126 MHz, CDCl3) δ 170.65, 77.96, 74.12, 68.85, 68.48, 60.92, 28.02, 25.74, 14.33.

[0274] The NMR data for product P54 are as follows:

[0275] 1 H NMR (500 MHz, CDCl3) δ 4.96 (s, 1H), 4.77 (d, J = 5.9 Hz, 1H), 4.58 (d, J = 5.9 Hz, 1H), 4.35 (ddd, J = 7.6, 6.2, 1.1 Hz, 1H), 4.21 (qd, J = 7.1,1.3 Hz, 2H), 4.10 (dd, J = 29.3, 16.4 Hz, 2H), 3.58 (qd, J = 9.5, 7.2 Hz,2H), 3.32 (s, 3H), 1.48 (s, 3H), 1.31 (s, 3H), 1.28 (t, J = 7.1 Hz, 3H).

[0276] 13 C NMR (126 MHz, CDCl3) δ 170.39, 112.57, 109.53, 85.23, 84.97,82.13, 72.45, 68.62, 61.03, 55.09, 26.59, 25.11, 14.33.

[0277] The NMR data for product P55 are as follows:

[0278] 1 H-NMR (500 MHz, CDCl3) δ ppm 4.22 (q, J = 7.2 Hz, 2H), 4.10 (s,2H), 3.48 (t, J = 7.5 Hz, 2H), 2.99 (p, J = 6.7 Hz, J. 2H. (t 2H), 1.28 (t, J = 7.2 Hz, 3H), 1.00 (d, J = 6.6 Hz, 12H).

[0279] 13 C NMR (126 MHz, CDCl3) δ 170.73, 73.21, 68.83, 60.95, 49.63, 44.81, 20.85, 14.36。

Claims

1. A copper catalyst, characterized in that, It comprises carbonized coffee grounds and copper ions, wherein the copper ions are loaded onto the carbonized coffee grounds; the copper ions include monovalent copper ions and divalent copper ions; preferably, the copper catalyst is composed of the carbonized coffee grounds and the copper ions; the copper ions are composed of monovalent copper ions and divalent copper ions.

2. A copper catalyst, characterized in that, It is prepared by the following method: The copper catalyst was obtained by mixing copper salt, coffee grounds and solvent, centrifuging and calcining.

3. The copper catalyst as described in claim 2, characterized in that, It satisfies one or more of the following conditions: (1) The copper salt is a divalent copper salt; such as one or more of copper chloride, copper sulfate, copper nitrate and copper acetate; for example, copper chloride; (2) The coffee grounds were purchased from FamilyMart convenience stores; (3) The mass ratio of the copper salt to the coffee grounds is (0.01-0.3):1; for example, (0.1-0.3):1; for example, 0.21:1; (4) The solvent is a solvent capable of dissolving the copper salt; such as one or more of water, methanol and ethanol; for example, water; the water is, for example, deionized water; (5) The mass-to-volume ratio of the coffee grounds and the solvent is 1 g / (10-30 ml); for example, 1 g / 20 ml; (6) The mixing is agitation mixing or ultrasonic mixing, for example, ultrasonic mixing; (7) The mixing time is 20-40 min, for example 30 min; (8) There is a drying step before calcination; the drying can be vacuum pump drying, and the drying time can be 5-7 hours; for example, 6 hours; (9) The calcination temperature is 600-800℃; for example, 700℃; (10) The calcination temperature is raised to the calcination temperature at a heating rate of 4-6℃ / min and then held; for example, the temperature is raised to the calcination temperature at a heating rate of 5℃ / min and then held. (11) The calcination time is 2-4 hours; for example, 3 hours; (12) The calcination is carried out under a protective atmosphere, for example, under an argon atmosphere; (13) The calcination is carried out in a tube furnace; (14) After the calcination is completed, the copper catalyst is naturally cooled to room temperature to obtain the copper catalyst; Preferably, the preparation method of the copper catalyst includes the following specific steps: ultrasonically mixing water, (0.1-0.3) equivalents of copper chloride and 1 equivalent of coffee grounds, centrifuging, drying, and calcining at 700°C under a protective atmosphere to obtain the copper catalyst.

4. The copper catalyst according to claim 2, characterized in that, The copper catalyst catalyzes the following coupling reaction: Include Fragment amine and containing The fragment reacts to form a diazo compound. ; Or; containing Fragment alcohol and containing The fragment reacts to form a diazo compound. .

5. The copper catalyst as described in claim 4, characterized in that, The containing The diazo compound of the fragment is a compound of formula I; the containing The amine of the fragment is a compound of formula II; the containing The alcohol fragment is a compound of formula IV; The copper catalyst catalyzes the following coupling reactions: the coupling reaction of compound I and compound II to generate compound III; or the coupling reaction of compound I and compound IV to generate compound V; ； ； Among them, R 1 -COOR 1-1 R 1-1 C 1-6 Alkyl or C 1-6 alkenyl; R 2 For H, C 6-14 aryl, 5-6 membered heteroaryl, with one or more R 2-1 Replacement C 6-14 aryl or aryl with one or more R 2-2 Substituted 5-6 aryl groups; R 2-1 and R 2-2 C, each independently 1-6 Alkyl, C 1-6 Alkoxy, halogen or C 1-6 Halogenated alkyl groups; R 3 C 1-6 Alkyl, C 6-14 aryl, with one or more R 3-1 Replacement C 1-6 Alkyl or with one or more R 3-2 Replacement C 6-14 Aryl; R 3-1 and R 3-2 Selected independently from C 6-14 Aryl, 5-15 membered heteroaryl, 5-10 membered heterocycloalkyl, C 5-7 Cycloalkenyl, C 1-6 Alkyl, C 1-6 Alkyl groups and those with one or more R groups 3-1-1 Replacement C 6-14 Aryl; R 3-1-1 C 1-6 Alkyl, C 1-6 Alkoxy, halogen or C 1-6 Halogenated alkyl groups; R 4 For H or C 1-6 alkyl; Or, R 3 R 4 It forms 5-10 membered heterocyclic alkyl groups, 5-15 membered heteroaryl groups with the N atoms therein, and is bonded by one or more R atoms. 4-1 Substituted 5-10 membered heterocyclic alkyl groups, with one or more R 4-2 Substituted 5-15 aryl or ;R 4-1 and R 4-2 Selected independently from C 6-10 Aryl, 5-15 quinone heteroaryl, C 1-6 Alkyl, oxy, and one or more R 4-1-1 Replacement C 6-10 aryl, with one or more R 4-1-2 Substituted 5-15 aryl groups and one or more R 4-1-3 Replacement C 1-6 Alkyl; R 4-1-1 R 4-1-2 and R 4-1-3 Selected independently from -SR 4-1-1-1 C 6-10 aryl, with one or more R 4-1-1-2 Replacement C 6-10 aryl and -OR 4-1-1-3 Ring A is a 5-10 membered heterocyclic alkyl group; ring B is formed by one or more R groups. 4-1-1-4 Substituted 5-15 aryl groups; R 4-1-1-1 and R 4-1-1-3 Selected independently from C 6-10 aryl, 5-15 quinone heteroaryl and one or more C 1-6 Alkyl-substituted C 6-10 Aryl; R 4-1-1-2 and R 4 -1-1-4 Each is a halogen, independent of the others; R 5 C 1-6 Alkyl, C 6-14 Aryl, 5-15 quinone heteroaryl, C 5-18 cycloalkyl, C 5-18 Cycloalkenyl, 5-10 membered heterocyclic alkyl, with one or more R 5-1 Substituted C1-6 alkyl, with one or more R 5-2 Replacement C 5-18 cycloalkyl, with one or more R 5-3 Replacement C 5-18 Cycloalkenyl or with one or more R 5-4 Substituted 5-10 membered heterocyclic alkyl groups; R 5-1 -R 5-4 Selected independently from C 1-8 Alkyl, C 6-14 Aryl, -COO-C 1-6 Alkyl, 5-15-membered heteroaryl, with one or more R 5-1-1 Replacement C 1-6 Alkyl group, by one or more R 5-1-2 Replacement C 6-14 aryl, with one or more R 5-1-3 Substituted 5-10 membered heterocyclic alkyl groups and NR 5-1-4 R 5 -1-5 ;R 5-1-1 -R 5-1-5 Selected independently from C 6-14 Aryl, halogen and C 1-6 Alkyl group.

6. The copper catalyst as described in claim 5, characterized in that, It meets one or more of the following conditions: (1) R 1 For COOMe, COOEt, COOBn or ; (2) R 2 For Ph, , , , , , , , , Or H; (3) R 3 for , , , , , , , , , , , , , , , , , , or ; (4) R 4 For H or Me; (5) R 3 R 4 Forming with the N atoms in between , , , , , or ; (6) R 5 for , , , , , , , , , , , , , or .

7. The copper catalyst as described in claim 5, characterized in that, It meets one or more of the following conditions: (1) The compound of formula I is , , , , , , , , , , , or ; (2) The compound of formula II is , , , , , , , , , , , , , , , , , , , , , , , , , , or ; (3) The compound of formula IV is , , , , , , , , , , , , , or ; (4) The compound of formula III is , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or ; (5) The compound of formula V is , , , , , , , , , , , , , or .

8. The copper catalyst according to claim 4, characterized in that, It meets one or more of the following conditions: (1) In the coupling reaction, the substance containing The fragment of the diazo compound and the containing The molar ratio of the amine fragments is (0.8-1.2):1; for example, 1:

1. (2) In the coupling reaction, the substance containing Fragments of diazo compounds and containing The molar ratio of the alcohol in the fragment is (1.5-2.5):1; for example, 2:

1. (3) In the coupling reaction, the copper catalyst and the catalyst containing... The mass-to-molar ratio of the diazo compound in the fragment is (15-25) g / 1 mol; for example, 20 g / 1 mol. (4) The coupling reaction also includes a solvent, which is a halocarbon solvent; for example, DCE; (5) The reaction temperature of the coupling reaction is 50-70℃; for example, 60℃; (6) The coupling reaction is carried out under a protective atmosphere; for example, under a nitrogen atmosphere; (7) The reaction time of the coupling reaction is 8-16 hours, for example 12 hours; (8) In the coupling reaction, the reactants of the coupling reaction consist of the following: the mixture containing... The fragment of the diazo compound, the one containing Fragment of amine or the contained The fragment of alcohol, the copper catalyst, and the solvent.

9. A method for preparing a copper catalyst, characterized in that, It includes the following steps: The copper catalyst was obtained by ultrasonication, centrifugation, and calcination of a mixture of copper salt, coffee grounds, and solvent. The conditions and operations of the steps are as described in claim 2 or 3; the definitions of the copper salt, coffee grounds, and solvent are as described in claim 2 or 3.

10. The use of a copper catalyst as described in claim 1 or as described in claim 2 or 3 in a catalytic coupling reaction, wherein the conditions and operation of the coupling reaction are as described in any one of claims 4-8.

11. Compounds with the following structural formulas: 。

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