Method for quinone hydroxylation reaction of alkene under catalysis of iron

Abstract

The invention discloses a method for catalyzing quinone hydroxylation reaction of alkene by iron, which comprises the following steps: in a solvent, by taking a quinone compound as a substrate, an alkene compound as a hydroxylation substrate, peroxide as an oxidizing agent, iron as a catalyst and amino acid or a derivative thereof as a ligand, catalyzing dehydrogenation coupling of an alkene C (sp2)-H bond and the quinone compound, the alcoholized quinone compound is generated. The method has the advantages that the catalyst is wide in source, cheap and environment-friendly; the oxidant is wide in source and cheap; reaction conditions are mild, and selectivity is high; the compatibility with functional groups of alkene compound substrates is good, and the application range of the substrates is wide; and carrying out free radical addition on the alkene compound through the high-valence iron oxide to generate a target product. Under optimized reaction conditions, the yield of the separated target product can reach 90%.

Description

Technical Field

[0001] The invention belongs to the field of catalytic synthesis technology and fine chemical synthesis, and specifically relates to a method for iron-catalyzed quinone hydroxylation of alkenes, especially a method for iron-catalyzed carbon hydroxylation of alkenes and dehydrogenation coupling of quinone compounds, which is a method for realizing iron-catalyzed carbon hydroxylation of alkenes and dehydrogenation coupling of quinone compounds by oxidizing a suitable oxidant with iron. Background Art

[0002] Catalytic ene functionalization provides a method for converting readily available petrochemical raw materials into valuable synthetic building blocks. Due to their unique electron and proton transfer properties, substituted naphthoquinones play an important role in biological systems and have anti-inflammatory, antifungal, antibacterial, antibiotic, antithrombotic, antiallergic and antiplatelet activities. Considering the availability of naphthoquinones, directly replacing carbon-hydrogen bonds with carbon-carbon bonds has become an attractive and efficient synthesis method (Cao L, Long H, Guan H, et al. Tetrahedron Letters, 2019, 60 (18): 1268-1271.). However, in previous methods, most of the hydroxyl sources came from oxygen, and the compatibility with olefin substrates was poor, the reaction time was long (Wang DM, She LQ, Yuan H, et al. Angewandte Chemie International Edition, 2023, 62(35): e202304573.), and the use of precious metal catalysts (Dong J, Yue F, Liu J, et al. Green Chemistry, 2021, 23(20): 7963-7968.), all of which severely limited the large-scale application of this method. Summary of the invention

[0003] Purpose of the invention: In view of the problems existing in the prior art, the present invention provides a method for the quinone hydroxylation reaction of olefins catalyzed by iron, which solves the problems of harsh conditions and the use of precious metal catalysts in the method for the quinone hydroxylation reaction of olefins catalyzed by iron, resulting in low total reaction yield, poor functional group compatibility, narrow scope of application, high waste discharge, and environmental protection, unsafety, and uneconomical. The method of the present invention only requires one step of reaction, does not require the participation of acid and alkali, and has the characteristics of a wide source of catalysts, low cost and environmental protection; the oxidant is cheap and does not produce any waste; the hydroxylation agent is mild, stable and cheap; the substrate source is wide and stable; the reaction conditions are mild, the selectivity is good and the yield is high; the substrate functional group compatibility is good and the scope of application of the substrate is wide; complex molecules and natural products are compatible, and the method for the quinone hydroxylation reaction of olefins catalyzed by iron can be well realized.

[0004] Technical solution: In order to achieve the above-mentioned purpose, the method of the iron-catalyzed quinone hydroxylation reaction of olefins of the present invention comprises the following steps: adding olefin compounds, quinone compounds and peroxides as oxidants, iron as catalysts, and amino acids or their derivatives as ligands in a solvent to generate alcoholized quinone compounds;

[0005] The general reaction formula is as follows:

[0006]

[0007] In the formula: R1 represents the substituent on the aromatic group in the aromatic hydrocarbon of the quinone compound, and R1 is an electron-donating group or an electron-withdrawing group; R2 represents the substituent on the 2nd position of the quinone compound, and R2 is an electron-donating group or an electron-withdrawing group;

[0008] R is hydrogen, alkyl or carbonyl, R' is hydrogen, alkyl, carbonyl, halogen, phenyl, benzyl, ester or hydroxyl. Wherein, R1 represents hydrogen, C1-C5 alkyl, hydroxyl, methoxyl, R2 represents hydrogen, C1-C5 alkyl, amino, hydroxyl, ester, methoxyl, ethoxyl, isopropyl or halogen.

[0009] Wherein, R represents C1-C5 alkyl, carbonyl or hydrogen, and R' represents hydrogen, C1-C5 alkyl, halogen, phenyl, benzyl, ester group, hydroxyl or tert-butyloxycarbonyl.

[0010] Preferably, R is hydrogen, methyl, ethyl, isopropyl; R' is tert-butyloxycarbonyl, ester, hydroxyl, C1-C3 alkyl.

[0011] Furthermore, R1 is C1-C2 alkyl, methoxy, hydroxyl; R2 is hydrogen, halogen, methoxy, ethoxy, isopropyl, hydroxyl or amino; R is C1-C4 alkyl or hydrogen; R' is C1-C4 alkyl, carbonyl, hydroxyl, ester or aryl.

[0012] Wherein, R1 is preferably methyl, methoxy, hydroxyl; R2 is preferably methyl, ethyl, isopropyl, hydroxyl, amino; R is preferably hydrogen, C1-C4 alkyl. R' is C1-C4 alkyl, carbonyl, hydroxyl, ester group, benzyl.

[0013] Wherein, the iron is selected from any one of ferrous trifluoromethanesulfonate, ferrous trifluoromethanesulfonate, ferrous chloride, ferrous acetylacetonate, ferrous acetylacetonate, ferrous 2,2,6,6-tetramethyl-3,5-heptanedione, ferrous 2,2,6,6-tetramethyl-3,5-heptanedione, ferrous 1,3-diphenylpropanedione, ferrous 1,3-diphenylpropanedione, ferrous benzoylacetonate, ferrous benzoylacetonate, ferrous ferrocyanide, ferrous ferrocyanide, ferrous acetate, ferrous sulfate, ammonium ferrous sulfate, ferrous sulfate, ferrous oxalate, ferrous oxalate, ferrous fluoride, ferrous fluoride, ferrous bromide, ferrous bromide, ferrous iodide, ferric iodide, ferric chloride, iron (III) perchlorate hydrate, 1,1'-bis(diphenylphosphino)ferrocene, ferrous phthalocyanine, ferric nitrate, ferric oxide or ferric oxide.

[0014] Wherein, the ligand is selected from any one of S-acetylaminomethyl-N-tert-butyloxycarbonyl-L-cysteine, N-acetyl-L-cysteine, N,N'-bis(tert-butyloxycarbonyl)-L-cystine, L-serine, D-cystine, aspartic acid, D-arginine, isoserine, L-threonine, L-tyrosine, BOC-L-proline, BOC-glycine-glycine-glycine, 2-allyl-N-FMOC-L-glycine, BOC-D-phenylalanine, L-cysteine, D-serine, D-proline, D-valine, L-proline, L-phenylalanine, N-BOC-N'-trityl-L-histidine, L-tryptophan, N-BOC-L-leucine, L-histidine, BOC-L-glutamate, L-cystine, or L-homocysteine.

[0015] Wherein, the oxidant is selected from any one of potassium persulfate, ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide, hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, benzoyl peroxide, tert-butyl benzoyl peroxide, di-tert-butyl peroxide, potassium monopersulfate, diisopropylbenzene peroxide, 2-methyl ethyl peroxide or bis(trimethylsilyl)peroxide.

[0016] Wherein, the solvent is an organic solvent, water or an aqueous solution of an organic solvent, and the organic solvent is selected from any one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1,3-propylene glycol, glycerol, n-butanol, isobutanol, tert-butanol, trifluoroethanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, tert-amyl alcohol, 4-methyl-2-pentanol, isopentanol, 2-pentanol, 3-pentanol, cyclopentanol, n-pentanol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, acetone, dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide, N,N-diformamide, N,N-diacetamide, ethyl acetate, 1,4-dioxane or tetrahydrofuran. When the solvent is an aqueous solution of an organic solvent, the volume ratio of the organic solvent to water is 1:(0.1-5).

[0017] The olefin compounds include electron-withdrawing, electron-donating internal olefin compounds, or electron-withdrawing, electron-donating terminal olefin compounds.

[0018] The molar ratio of the quinone compound, olefin compound, peroxide, amino acid or its derivative, and iron catalyst is 1:(0.5-50):(2-50):(0.002-20):(0.001-10); the reaction temperature is 25-150°C and the reaction time is 0.25-24 hours.

[0019] Preferably, the molar ratio of the quinone compound, olefin compound, peroxide, amino acid or its derivative, and iron catalyst is 1:(2-5):(2-10):(0.002-10):(0.001-5); the reaction temperature is 25-100°C and the reaction time is 0.25-3 hours.

[0020] The iron catalyst in the method of the present invention has the characteristics of large natural abundance, low price and low toxicity. A specific amino acid ligand is used to coordinate with the iron catalyst to form a highly active catalytic species. This catalytic species works together with an oxidant, a solvent, etc. to form an alkyl radical to attack a quinone reagent, which has high activity and selectivity. In addition, the method of the present invention uses a mild reagent and a mild environment to solve the problem of harsh reaction conditions; solves the problem of olefin hydroxylation; the reaction directly attacks the quinone reagent without pre-functionalization, iron is a catalyst, no precious metals are used, and the effect is remarkable. The method of the present invention has the advantages of a wide source of catalysts, low cost and environmental protection; a wide source of oxidants, low cost; mild reaction conditions, high selectivity; good compatibility of substrate functional groups and a wide range of application of substrates; drug molecules and drug molecule derivatives are compatible, and can well realize alcoholization quinone reactions. Under optimized reaction conditions, the yield of the target product after separation can reach 90%.

[0021] The present invention first oxidizes low-valent iron into high-valent iron by an oxidant, and generates corresponding high-valent iron oxides. The high-valent iron electrophilic oxidant attacks olefin compounds to generate alkyl free radicals, and the alkyl free radicals undergo free radical addition with the olefinic bonds of naphthoquinone to generate quinone compound free radicals of alkyl alcohols. Finally, the high-valent iron obtains electrons and is converted into low-valent iron, and then the quinone compounds of alcohols are deprotonated to obtain alcoholized quinone compounds, thereby completing the catalytic cycle. The method of the present invention has achieved good results and provides a new method and a new mechanism for the hydroxylation reaction of carbon in olefin compounds. By introducing amino acids or their derivatives and coordinating with iron catalysts, the activity and selectivity of iron catalysis are improved, thereby solving a series of problems existing in the purification reaction of quinones, such as harsh reaction parts, low reaction efficiency, harsh reaction conditions, and the need to use noble metal catalysts. The present invention uses amino acids as ligands to make iron reach a more suitable activity, and too high activity is prone to more by-products, and low activity has a lower yield. The present invention generates a target product by free radical addition of a high-valent iron oxide compound to an olefin compound, and improves the activity of iron by the coordination of an amino acid to iron, thereby improving the compatibility with substrates. This type of reaction is basically incompatible with internal alkenes, while the method of the present invention can achieve compatibility with various types of internal alkenes.

[0022] At present, there are few reports on alcoholized quinones. The compatibility of olefin compounds is limited to styrene compounds, which is achieved through copper catalysis and sulfate as an oxidant. However, the method of the present invention can supply oxygen to olefin compounds by coordinating iron with amino acid ligands to form high-valent iron oxides under the action of hydrogen peroxide, forming carbon free radicals, which are then captured by naphthoquinone and the target product is generated through addition elimination. In the carbon hydroxylation reaction of olefin compounds, the method of the present invention has better compatibility with substrate functional groups, is environmentally friendly, and has mild reaction conditions.

[0023] In addition, some of the methods for carbon hydroxylation of olefin compounds that have been reported so far require that the substrate needs to be coordinated with N element during the reaction process, so the methods of the prior art are obviously inferior to the present invention in terms of substrate compatibility. However, we can, under the action of hydrogen peroxide, generate high-valent iron oxide compounds by coordinating iron with amino acid ligands to supply oxygen to olefin compounds, forming carbon free radicals, which are then captured by naphthoquinone and the target product is generated by addition elimination. Therefore, the reaction mechanism of the method of the present invention has no requirements on the functional groups of the reaction substrate, has good reaction activity, and has a short reaction time. At the same time, if the activity after the coordination of iron and amino acids is too high, many side effects will occur, and the activity is low and the yield is low. The present invention can further achieve a more suitable activity of iron by regulating the amino acid ligands, so as to achieve the purpose of expanding substrate compatibility.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0025] (1) The present invention provides a method for the iron-catalyzed quinone hydroxylation of olefinic compounds promoted by amino acid and derivative ligands. The method requires only one step of reaction, does not require the participation of acid or base, and has the unique advantages of cheap catalysts, ligands and oxidants, wide sources and environmental protection; mild reaction conditions and high selectivity; wide, stable and easy to handle substrate sources; good compatibility of substrate functional groups and wide application range of substrates; experimental results prove that the reaction is suitable for alcoholization of quinone reactions, and there is no good method in the prior art to form highly active catalyst species;

[0026] (2) The method for alcoholization of quinones provided by the present invention is simple, easy and safe, has good compatibility and selectivity for electron-withdrawing olefin compounds, and under optimized reaction conditions, the yield of the target product after separation can reach 90%. In addition, the reaction time is short, the conditions are mild, and the reaction cost is better reduced. It is a general, efficient, economical and environmentally friendly method for hydroxylating quinones;

[0027] (3) The reason why the method of the present invention can use ideal iron as a catalyst for the reaction is that the key is the use of amino acid ligands, which are coordinated with the iron catalyst to form a highly active catalytic species, so that the reaction can be carried out under very mild conditions. Quinone alcoholization reaction, especially for drug molecules and their derivatives, can also achieve an ideal catalytic effect.

[0028] (4) The alcoholized quinone compounds synthesized by the method of the present invention can be used as drugs or bioactive molecules, and are also important organic intermediates, and are widely used in the synthesis of pharmaceutical intermediates and high value-added fine chemicals. DETAILED DESCRIPTION

[0029] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0030] The experimental methods described in the examples are conventional methods unless otherwise specified; the reagents and materials described can be obtained from commercial sources or simply prepared by existing technologies unless otherwise specified.

[0031] The specific structures of the substrates and products in the examples are shown in Table 1.

[0032] The substrates 1a-1aa used in Example 1 of the present invention are all known compounds. The remaining substrates are allyl-protected phenolic hydroxyl raw material compounds or allyl-protected carboxyl raw material compounds.

[0033] Among them, the general method for synthesizing allyl-protected phenolic hydroxyl raw materials is:

[0034] In nitrogen, phenol compound (1 mmol), TBAI (0.1 mmol), K2CO3 (2 mmol), DMF (2 mL) were added to the reaction flask in sequence, mixed evenly at room temperature, and then allyl bromide (1.5 mol) was added. The reaction mixture was stirred at room temperature for 12 h. After the reaction was completed, the product was directly separated by chromatography.

[0035] Among them, the synthesis method of allyl protected carboxyl raw materials:

[0036] In nitrogen, carboxylic acid compound (1 mmol), TBAI (0.1 mmol), K2CO3 (2 mmol), DMF (2 mL) were added to the reaction flask in sequence, mixed evenly at room temperature, and then allyl bromide (1.1 mol) was added, and the reaction mixture was stirred at room temperature for 12 h. After the reaction was completed, the product was directly separated by chromatography.

[0037] Among them, compound 1 (CAS: 2306477-06-3) and compound 2 (CAS: 2306477-07-4) synthesized in the example are both known compounds.

[0038] Example 1

[0039] Synthesis of compound 1

[0040] In air, ferric bromide (0.05mmol), D-serine (0.1mmol), substrate 1a (1mmol), CH3CN (2.0mL), H2O (2.0mL), 1,4-naphthoquinone (0.5mmol) and potassium monopersulfate (4mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80℃ for 3h. After the reaction was completed, the product 1 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:5) with a yield of 90%.

[0041] Example 2

[0042] Synthesis of compound 2

[0043] In air, ferric chloride (0.1 mmol), L-homocystine (0.2 mmol), substrate 1b (1 mmol), methanol (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and diisopropylbenzene peroxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60 ° C for 3 h. After the reaction was completed, the product 2 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:3) with a yield of 85%.

[0044] Example 3

[0045] Synthesis of compound 3

[0046] In air, ferrous trifluoromethanesulfonate (0.04mmol), aspartic acid (0.08mmol), substrate 1c (1mmol), tert-butyl alcohol (2.0mL), 1,4-naphthoquinone (0.5mmol) and di-tert-butyl peroxide (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 75℃ for 3h. After the reaction was completed, the product 3 was directly separated by chromatography (petroleum ether: dichloromethane V / V=10:2) with a yield of 88%.

[0047] 1 H NMR (400MHz, CDCl3) δ8.16–8.07(m,2H),7.77(dt,J=5.5,4.0Hz,2H),6.95(d,J=0.6Hz,1H),4.46(d,J=11.4Hz,1H),3.78–3.65(m,1H),3.1 7(td,J=11.6,3.5Hz,1H),2.73(ddt,J=14.0,4.3,2.2Hz,1H),2.59–2.49(m,1H),2.27–2.16(m,1H),2.02–1.93(m,1H),1.93–1.77(m,2H). 13 C NMR(101MHz, CDCl3)δ209.3,185.1,184.7,149.9,135.1,133.9,133.9,132.4,131.8,126.8,126.1,77.2,49.6,39.2,30.3,20.0.HRMS(ESI)calcd.forC 16 H 15 O4 + [M+H] + m / z 271.0965, found 271.0965;

[0048] Example 4

[0049] Synthesis of compound 4

[0050] In air, ferrous chloride (0.5mmol), S-acetylaminomethyl-N-tert-butyloxycarbonyl-L-cysteine ​​(1.0mmol), substrate 1d (1mmol), isopropanol (1.5mL) and water (2.5mL), 1,4-naphthoquinone (0.5mmol) and hydrogen peroxide (1.5mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 100℃ for 1h. After the reaction was completed, 5mL of water was added, and extracted with ethyl acetate (5mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then separated by column chromatography (petroleum ether: dichloromethane V / V=10:4) to obtain product 4 with a yield of 65%.

[0051] 1 H NMR(400MHz, CDCl3)δ8.16–8.04(m,2H),7.80–7.72(m,2H),6.94(s,1H),4.06–3.9 7(m,1H),3.79–3.53(m,2H),3.48–3.33(m,1H),1.71(s,1H),1.30(d,J=7.1Hz,3H). 13 CNMR (100MHz, CDCl3) δ185.6,185.0,185.9,152.4,152.0,136.1,135.9,134.0,134.9,133.9,133.8,13 2.2,131.8,126.9,126.9,126.1,1256.1,74.4,73.0,48.9,48.6,36.4,16.6,13.5.HRMS(ESI)calcd.for C 14 H 14 ClO3 + [M+H] + m / z 265.0626, found 265.0618;

[0052] Example 5

[0053] Synthesis of compound 5

[0054] In air, ferrous acetylacetonate (0.02mmol), BOC-L-glutamic acid (0.04mmol), substrate 1e (1mmol), glycerol (1.5mL) and water (0.5mL), 1,4-naphthoquinone (0.5mmol) and peracetic acid (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60℃ for 2h. After the reaction was completed, 5mL of water was added, and ether was extracted (5mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was performed (petroleum ether: ethyl acetate V / V=10:2) to obtain product 5 with a yield of 73%.

[0055] Example 6

[0056] Synthesis of compound 6

[0057] In air, ferric acetylacetonate (0.08 mmol), L-tyrosine (0.16 mmol), substrate 1f (1 mmol), n-butanol (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and tert-butyl hydroperoxide (5 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 25 ° C for 3 h. After the reaction was completed, the product 6 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:1) with a yield of 70%.

[0058] 1 H NMR (400MHz, CDCl3) δ7.96 (dd, J = 22.9, 3.9Hz, 2H), 7.71–7.60 (m, 2H), 6.92 (s, 1H), 3.92 (s, 4H), 3.36 (s, 1H), 3.30–2.58 (m, 2H). 13 C NMR(100MHz, CDCl3)δ185.0,184.9,149.2,136.2,133.9,133.9,132.1,131.7,126.8,126.1,63.3,42.2.HRMS(ESI)calcd.forC 13 H 13 O4 + [M+H] + m / z 233.0809, found 233.0809

[0059] Example 7

[0060] Synthesis of compound 7

[0061] Iron trifluoromethanesulfonate (0.05mmol), L-cystine (0.1mmol), substrate 1g (1mmol), acetonitrile (2.0mL), 1,4-naphthoquinone (0.5mmol) and m-chloroperbenzoic acid (1.5mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 50°C for 1h. After the reaction was completed, the product 7 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 20:3) with a yield of 87%.

[0062] 1H NMR (400MHz, CDCl3) δ8.02(ddd,J=8.7,7.0,3.4Hz,2H),7.69(dd,J=5.4,3.4Hz,2H),6.92(s,1H),5.04(s,1H), 3.81(d,J=8.9Hz,2H),3.70(s,1H),3.48(dt,J=14.7,7.5Hz,1H),3.41–3.30(m,1H),3.23(s,1H),1.40(s,9H). 13 C NMR (101MHz, CDCl3) δ184.8,184.6,157.5,149.6,135.8,133.8,133.9,132.1,131.8,126.8,126.1,80.4,60.8,40.5,39.8,28.3.HRMS(ESI)calcd.for C18H22NO5+[M+H]+m / z 330.1347,found330.1343;

[0063] Example 8

[0064] Synthesis of compound 8

[0065] In air, ferrous fluoride (0.1mmol), N,N'-bis(tert-butyloxycarbonyl)-L-cystine (0.4mmol), substrate 1h (1mmol), acetonitrile (1.5mL) and water (1.5mL), 1,4-naphthoquinone (0.5mmol) and potassium persulfate (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80℃ for 2h. After the reaction was completed, 5mL of water was added, and extracted with ethyl acetate (5mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was separated (petroleum ether: ethyl acetate V / V=10:3) to obtain product 8 with a yield of 76%.

[0066] 1 H NMR(400MHz, CDCl3)δ8.05(ddd,J=9.0,6.1,3.4Hz,2H),7.77–7.69(m,2H),7.26(t,J=7.4Hz,3H),7.19( d,J=7.3Hz,2H),3.79(d,J=5.4Hz,2H),3.56(dd,J=9.3,3.7Hz,1H),2.97(ddd,J=35.9,13.8,7.6Hz,2H). 13C NMR (100MHz, CDCl3) δ185.0,158,151.3,138.8,135.8,133.8,133.7,132.2,131 .8,129.02,128.6,126.8,126.5,126.1,63.9,42.4,36.1.HRMS(ESI)calcd.for C 19 H 17 O3 + [M+H] + m / z 293.1172, found 293.1171;

[0067] Example 9

[0068] Synthesis of compound 9

[0069] In air, ferrous iodide (0.08 mmol), N-acetyl-L-cysteine ​​(0.32 mmol), substrate 1i (1 mmol), trifluoroethanol (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and benzoyl peroxide (2 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60 ° C for 2 h. After the reaction was completed, the product 9 was directly separated by chromatography (petroleum ether: dichloromethane V / V = 10:5) with a yield of 74%.

[0070] 1 H NMR (400MHz, CDCl3) δ8.14–8.03(m,2H),7.79–7.70(m,2H),7.26–7.20(m,2H),7.17–7.11(m,3H),6.83(dd,J=9.9,5 .6Hz,1H),3.86–3.75(m,2H),3.27(dq,J=8.8,5.9Hz,1H),2.74–2.57(m,2H),2.13–2.02(m,1H),2.01–1.90(m,1H). 13 C NMR (100MHz, CDCl3) δ185.3,185.0,151.,141.3,135.5,133.9,133.8,132.3,131. 9,128.5,128.4,126.8,126.1,126.0,65.3,40.8,33.7,31.8.HRMS(ESI)calcd.for C 20 H 19 O3 + [M+H] + m / z 307.1329, found 307.1332.

[0071] Example 10

[0072] Synthesis of compound 10

[0073] Under nitrogen atmosphere at normal pressure, ferrous sulfate (0.05 mmol), L-cysteine ​​(0.1 mmol), substrate 1j (1 mmol), dimethyl sulfoxide (1.5 mL) and water (0.5 mL), 1,4-naphthoquinone (0.5 mmol) and sodium persulfate (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 °C for 1 h. After the reaction was completed, 5 mL of water was added, and the mixture was extracted with ethyl acetate (5 mL × 3). The organic phases were combined and washed with water (5 mL × 3). The organic phases were collected, the solvent was evaporated under reduced pressure, and then separated by column chromatography (petroleum ether: ether V / V = 10:2) to obtain product 10 with a yield of 70%.

[0074] 1 H NMR (400MHz, CDCl3) δ8.09(s,1H),8.01(s,1H),7.96(d,J=7.4Hz,2H),7.72(s,2H),7.53(d,J=6.9Hz,1H),7.40(t,J= 7.2Hz, 2H), 6.96 (s, 1H), 4.64 (d, J=5.1Hz, 2H), 3.92 (ddd, J=16.3, 10.9, 5.8Hz, 2H), 3.72–3.63 (m, 1H), 2.77 (s, 1H). 13 C NMR (100MHz, CDCl3) δ184.7,184.5,166.8,148.3,136.3,134.0,133.9,133.4,132. 1,131.8,129.7,129.4,128.5,126.9,126.2,63.1,61.3,40.2.HRMS(ESI)calcd.for C 20 H 17 O5 + [M+H] + m / z337.1071, found 337.1069;

[0075] Embodiment 11

[0076] Synthesis of compound 11

[0077] Under normal pressure nitrogen, 2,2,6,6-tetramethyl-3,5-heptanedione ferrous acid (0.02mmol), L-serine (0.04mmol), substrate 1k (1mmol), dimethyl sulfoxide (4.0mL), 1,4-naphthoquinone (0.5mmol) and tert-butyl benzoyl peroxide (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 25°C for 1h. After the reaction was completed, 5mL of water was added, and extracted with ethyl acetate (5mL×3), the organic phases were combined, washed with water (5mL×3), and the organic phases were collected. The solvent was evaporated under reduced pressure and separated by column chromatography (petroleum ether: ether V / V=10:5) to obtain product 11 with a yield of 79%.

[0078] 1 H NMR (400MHz, CDCl3) δ8.05(ddd,J=13.6,5.5,3.4Hz,2H),7.74(dd,J=5.5,3.4Hz,2H),6.84(s,1H),3.84(p, J=11.2Hz,2H),3.55–3.43(m,1H),3.17(dd,J=13.9,6.8Hz,1H),3.04(dd,J=13.7,7.8Hz,1H),2.01(s,1H). 13 C NMR (101MHz, CDCl3) δ184.8,149.7,136.0,134.1,134.0,132.0,131.7,126.8,126.2,63.7,41.2,23.4. 19 F NMR(376MHz, CDCl3)δ-142.30(dd,J=14.7,9.0Hz),-155.75(td,J=20.9,4.7Hz),161.68–-162.14(m).HRMS(ESI)calcd.for C 19 H 12 F5O3 + [M+H] + m / z 383.0701, found 383.0705.

[0079] Example 12

[0080] Synthesis of compound 12

[0081] In air, ferrous acetate (0.02 mmol), D-cystine (0.04 mmol), substrate 1l (1 mmol), dichloromethane (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and 2-butanone peroxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 25 ° C for 0.5 h. After the reaction was completed, the product 12 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:3) with a yield of 86%.

[0082] 1 H NMR (400MHz, CDCl3) δ8.15–8.05(m,2H),7.79–7.73(m,2H),6.86(d,J=0.6Hz,1H),3.82–3.80(m,1H) ,3.54(t,J=6.6Hz,2H),3.30–3.22(m,1H),1.86–1.75(m,4H),1.69–1.59(m,2H),1.54–1.43(m,2H). 13 C NMR (100MHz, CDCl3) δ185.27,185.02,151.84,135.42,133.87,133.78,132.28,131. 86,126.85,126.07,65.04,44.67,40.69,32.38,29.42,24.61.HRMS(ESI)calcd.for C 16 H 18 ClO3 + [M+H] + m / z 293.0939, found 293.0939

[0083] Embodiment 13

[0084] Synthesis of compound 13

[0085] In air, ferrous ferrocyanide (0.001mmol), BOC-glycine-glycine-glycine (0.002mmol), substrate 1m (0.5mmol), 1,2-dichloroethane (2.0mL), cyclopentene (1mmol) and bis(trimethylsilyl) peroxide (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 40°C for 1h. After the reaction was completed, the product 13 was directly separated by chromatography (petroleum ether: ether V / V = 10:5) with a yield of 90%.

[0086] 1H NMR (400MHz, CDCl3) δ8.11-7.99(m,2H),7.73-7.66(m,2H),4.66(dd,J=12.4,6.4Hz,1H),3.25-3.15(m, 1H), 2.34(dt,J=12.7,6.0Hz,1H),2.28(s,3H),2.05-1.95(m,2H),1.95-1.86(m,2H),1.77-1.71(m,1H). 13 C NMR(100MHz, CDCl3)δ185.0,185.0,148.0,145.0,133.4,133.3,132.6,131.9,126.2,126.1,78.7,50.3,36.6,31.0,23.9,12.9.HRMS(ESI)calcd.for C 16 H 17 O3 + [M+H] + m / z 257.1172, found 257.1178.

[0087] Embodiment 14

[0088] Synthesis of compound 14

[0089] In air, ferrous bromide (0.05mmol), BOC-D-phenylalanine (0.1mmol), substrate 1n (0.5mmol), acetonitrile (1.0mL) and water (1.0mL), cyclopentene (1mmol) and ammonium persulfate (1.5mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60°C for 2h. After the reaction was completed, 5mL of water was added, and extracted with ethyl acetate (5mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was performed (petroleum ether: ethyl acetate V / V=10:2) to obtain product 14 with a yield of 89%.

[0090] 1 H NMR (400MHz, CDCl3) δ8.07-7.91(m,2H),7.70-7.62(m,2H),4.60(dd,J=11.8,6.1Hz,1H),3.40(dt,J=14.1,7.0Hz,1H),3.32 -3.24(m,1H),2.33(dt,J=19.6,6.8Hz,1H),2.03-1.91(m,2H),1.90-1.81(m,2H),1.76-1.66(m,2H),1.38(d,J=7.0Hz,6H). 13CNMR (100MHz, CDCl3) δ185.30,184.54,150.49,147.39,133.4,133.3,132.6,132 .0,126.2,126.0,78.5,50.2,36.8,31.9,24.1,20.1,14.7.HRMS(ESI)calcd.for C 18 H 21 O3 + [M+H] + m / z 285.1485, found 285.1479.

[0091] Embodiment 15

[0092] Synthesis of compound 15

[0093] In a 25 mL reaction bottle under nitrogen atmosphere, 2,2,6,6-tetramethyl-3,5-heptanedione iron (0.1 mmol), D-arginine (0.2 mmol), substrate 1o (0.5 mmol), N,N-diformamide (2.0 mL), cyclopentene (1 mmol) and tert-butyl peroxide benzoyl ester (1.5 mmol) were added in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 ° C for 3 h. After the reaction was completed, 5 mL of water was added, and the mixture was extracted with ethyl acetate (5 mL × 3). The organic phases were combined, the solvent was evaporated under reduced pressure, and then separated by column chromatography (petroleum ether: ethyl acetate V / V = 10:1) to obtain product 15 with a yield of 70%.

[0094] 1 H NMR (400MHz, CDCl3) δ8.07-8.00(m,2H),7.73-7.66(m,2H),4.52(dd,J=13.0,6.7Hz,1H),4.13-4.08(m,3H),3 .39(ddd,J=9.3,7.9,5.3Hz,1H),2.26-2.15(m,1H),2.04-1.95(m,1H),1.88-1.83(m,2H),1.72-1.66(m,2H). 13 C NMR (100MHz, CDCl3) δ185.82,181.46,158.69,136.77,133.98,133.41,132.38,131. 58,126.43,126.19,78.43,61.71,45.52,36.38,30.66,23.72.HRMS(ESI)calcd.for C 16 H 17 O4+[M+H]+m / z 273.1122,found273.1124

[0095] Example 16

[0096] Synthesis of compound 16

[0097] In air, 1,3-diphenylpropanedione iron (0.05mmol), D-valine (0.1mmol), substrate 1p (0.5mmol), ethyl acetate (2.0mL), cyclopentene (1mmol) and tert-butyl hydroperoxide (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80℃ for 3h. After the reaction was completed, the product 16 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:2) with a yield of 81%.

[0098] Embodiment 17

[0099] Synthesis of compound 17

[0100] In air, 1,3-diphenylpropanedione ferrous acid (0.5 mmol), BOC-L-proline (1.5 mmol), substrate 1q (0.5 mmol), 1,4-dioxane (2.0 mL), cyclopentene (1 mmol) and hydrogen peroxide (1.5 mmol) were added to a 25 mL reaction bottle in sequence, and mixed evenly at room temperature. The reaction mixture was stirred at 100 ° C for 3 h. After the reaction was completed, the product 17 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 20:3) with a yield of 52%. 1 H NMR (400MHz, Acetone) δ8.10-8.01(m,2H),7.90-7.76(m,2H),4.64(dd,J=13.3,6.7Hz,1H),3.43(td,J=9.5,7.0H z,1H),2.12(dd,J=12.3,6.9Hz,1H),1.98-1.90(m,2H),1.83(dt,J=6.9,5.6Hz,2H),1.67(dd,J=12.3,6.4Hz,1H). 13 C NMR(100MHz,Acetone)δ206.4,206.0,185.3,135.5,135.4,133.9,133.7,130.8,1237.0,126.4,77.1,45.5,36.4,30.1,23.9.HRMS(ESI)calcd.for C 15 H 15 O4 + [M+H] + m / z 259.0965, found 259.0962.

[0101] Embodiment 18

[0102] Synthesis of compound 18

[0103] In air, ferrous benzoyl acetonate (0.05 mmol), D-proline (0.1 mmol), substrate 1r (0.5 mmol), tetrahydrofuran (2.0 mL), cyclopentene (1 mmol) and benzoyl peroxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 ° C for 3 h. After the reaction was completed, the product 18 was directly separated by chromatography (petroleum ether: dichloromethane V / V = 10:6) with a yield of 64%.

[0104] 1 H NMR (400MHz, CDCl3) δ8.02(t,J=8.2Hz,2H),7.68(td,J=7.5,1.2Hz,1H),7.59(t d,J=7.5,1.1Hz,1H),5.35(s,2H),4.63(dd,J=13.5,6.7Hz,1H),2.84(dd,J=16. 5,9.2Hz,1H),2.22(dd,J=12.6,6.6Hz,1H),2.12-2.03(m,1H),2.03-1.95(m,1H ),1.93-1.87(m,1H),1.84(dd,J=12.9,6.5Hz,1H),1.69(dd,J=12.6,6.8Hz,2H). 13 C NMR(100MHz, CDCl3)δ134.4,133.7,132.0,126.0,125.8,78.5,77.3,77.03,76.7,47.0,35.9,28.9,23.5.HRMS(ESI)calcd.for C 15 H 16 NO3 + [M+H] + m / z 258.1125, found 258.1125;

[0105] Embodiment 19

[0106] Synthesis of compound 19

[0107] In air, iron benzoyl acetonate (0.2 mmol), N-BOC-L-leucine (0.4 mmol), substrate 1s (0.5 mmol), sec-butyl alcohol (2.0 mL), cyclopentene (1 mmol) and peracetic acid (1.5 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60 ° C for 3 h. After the reaction was completed, the product 19 was directly separated by chromatography (petroleum ether: dichloromethane V / V = 10:5) with a yield of 48%.

[0108] 1 H NMR (400MHz, CDCl3) δ8.16-8.03(m,2H),7.78-7.71(m,2H),4.71(q,J=6.5Hz,1H),3.65-3.55(m,1H),2.3 0(td,J=13.8,6.9Hz,1H),2.09(dd,J=14.6,5.4Hz,1H),2.00-1.85(m,3H),1.73(dd,J=12.8,6.6Hz,1H). 13 C NMR (100MHz, CDCl3) δ182.7,148.8,144.2,134.3,133.9,132.1,131.1,127.1,127.0 78.3,50.9,36.6,30.4,23.8.HRMS(ESI)calcd.for C 15 H 14 ClO3 + [M+H] + m / z 277.0626, found 277.0446

[0109] Embodiment 20

[0110] Synthesis of compound 20

[0111] In air, ferric ferrocyanide (0.05 mmol), L-histidine (0.15 mmol), substrate 1t (0.5 mmol), polyethylene glycol-2000 (1.0 g) and water (1.0 mL), cyclopentene (1 mmol) and m-chloroperbenzoic acid (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 120 ° C for 3 h. After the reaction was completed, 5 mL of water was added, and ether was extracted (5 mL × 3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was separated (petroleum ether: ethyl acetate V / V = 10:3) to obtain product 20 with a yield of 70%.

[0112] 1H NMR (400MHz, CDCl3) δ8.17-8.04(m,2H),7.78-7.70(m,2H),4.74(dd,J=12.5,6.4Hz,1H),3.66(tdd,J=9.3,5 .9,3.1Hz,1H),2.39-2.26(m,1H),2.18-2.08(m,1H),2.02-1.87(m,3H),1.76(ddd,J=13.0,6.9,4.8Hz,1H). 13 C NMR (100MHz, CDCl3) δ181.95,177.54,152.34,140.43,134.16,133.89,131.98,130.78,127.45,127.02,78.51,54.74,36.65,30.66,23.84.H RMS(ESI)calcd.for C 15 H 14 BrO3 + [M+H] + m / z 321.0121, found 321.0116.

[0113] Embodiment 21

[0114] Synthesis of compound 21

[0115] In air, ferric iodide (0.05mmol), L-tryptophan (0.1mmol), substrate 1u (0.5mmol), 4-methyl-2-pentanol (2.0mL), cyclopentene (1mmol) and tert-butyl peroxide benzoyl ester (2mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80°C for 18h. After the reaction was completed, the product 21 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:1) with a yield of 51%.

[0116] 1 H NMR (400MHz, CDCl3) δ8.03-7.92(m,2H),7.65(dt,J=4.5,3.9Hz,2H),4.57(dd,J=11.9,6.1Hz,1H),3.38(p,J=8.9Hz,1 H),3.28(td,J=9.2,6.4Hz,1H),2.30(td,J=13.7,6.9Hz,1H),2.03-1.92(m,5H),1.90-1.78(m,6H),1.74-1.65(m,3H). 13C NMR (100MHz, CDCl3) δ185.3,184.7,152.3,1485,133.2,133.3,132.8,132.4,126.1,1 25.9,78.8,49.5,39.4,36.8,33.0,32.9,32.2,27.6,27.5,24.1.HRMS(ESI)calcd.for C 20 H 23 O3 + [M+H] + m / z 328.1907, found 328.1907;

[0117] Embodiment 22

[0118] Synthesis of compound 22

[0119] In air, ferrous oxalate (0.05 mmol), N-BOC-N'-trityl-L-histidine (0.1 mmol), substrate 1v (0.5 mmol), cyclopentanol (2.0 mL), cyclopentene (1 mmol) and di-tert-butyl peroxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80°C for 2 h. After the reaction was completed, the product 22 was obtained by direct chromatography (petroleum ether: ethyl acetate V / V = 10:1) with a yield of 65%.

[0120] Embodiment 23

[0121] Synthesis of compound 23

[0122] In air, iron oxide (0.1mmol), L-threonine (0.4mmol), substrate 1w (0.5mmol), isoamyl alcohol (2.0mL), cyclopentene (1mmol) and diisopropylbenzene peroxide (1.5mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80℃ for 3h. After the reaction was completed, the product 23 was obtained by direct chromatography separation (petroleum ether: ethyl acetate V / V = 10:4) with a yield of 63%.

[0123] 1H NMR (400MHz, CDCl3) δ8.08–7.96(m,2H),7.67(dd,J=6.4,2.6Hz,2H),4.64(q,J=6.2Hz,1H),3.18(dd,J=15.5,8.8Hz,1H ),2.35–2.27(m,1H),2.25(s,2H),2.00(ddd,J=20.0,11.0,6.7Hz,2H),1.92–1.82(m,2H),1.71(dt,J=19.4,6.7Hz,1H). 13 C NMR(100MHz, CDCl3)δ185.0,185.0,147.9,145.0,133.4,133.3,132.6,131.9,126.2,126.1,78.7,50.3,36.6,31.0,23.9,12.9.HRMS(ESI)calcd.for C 16 H 16 BrO3 + [M+H-HBr]+m / z 225.1016,found225.1012;

[0124] Embodiment 24

[0125] Synthesis of compound 24

[0126] In air, ferric sulfate (0.2 mmol), isoserine (0.5 mmol), substrate 1x (0.5 mmol), dimethyl sulfoxide (2.0 mL), cyclopentene (1 mmol) and 2-methylperoxide (2 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60 ° C for 1 h. After the reaction was completed, 5 mL of water was added, and ethyl acetate was extracted (5 mL × 3), the organic phases were combined, washed with water (5 mL × 3), and the organic phases were collected. The solvent was evaporated under reduced pressure and separated by column chromatography (petroleum ether: dichloromethane V / V = 10:8) to obtain product 24 with a yield of 71%.

[0127] 1NMR (400MHz, CDCl3) δ8.06(dd,J=14.2,7.4Hz,2H),7.72(dd,J=9.8,6.2Hz,2H),5.15(t,J=2.6Hz,2H),4.57(dd,J=12.9,6.6Hz,1H),3.45 (dd,J=15.7,8.9Hz,1H),2.56(t,J=2.2Hz,1H),2.24(dt,J=19.2,6.7Hz,1H),2.05-1.96(m,1H),1.96-1.83(m,3H),1.72(d,J=6.4Hz,1H). 13 C NMR (100MHz, CDCl3) δ185.3,181.2,155.9,138.6,134.0,133.4,132.3,131.2,126.4,126.2,78.3,78.2,76.9,60.6,45.8,36.1,30.9,23.6.13C NMR (100MHz, CDCl3) δ185.3,181.2,155.9,138.6,134.0,133.4,132.3,131.2,12 6.4,126.2,78.3,78.2,76.9,60.6,45.8,36.1,30.9,23.6.HRMS(ESI)calcd.for C 18 H 16 O4H+[M+H]+m / z297.1122,found 297.1123.

[0128] Embodiment 25

[0129] Synthesis of compound 25

[0130] In air, iron (III) perchlorate hydrate (0.15 mmol), 2-allyl-N-FMOC-L-glycine (0.3 mmol), substrate 1y (0.5 mmol), N,N-diacetamide (1.5 mL) and water (0.5 mL), cyclopentene (1 mmol) and hydrogen peroxide (2 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 ° C for 3 h. After the reaction was completed, ammonia water (0.5 mL, 25%) was added and stirred for 1 h. Then, 5 mL of water was added, and extracted with ether (5 mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was separated (petroleum ether: dichloromethane V / V=10:1) to obtain product 25 with a yield of 65%

[0131] Embodiment 26

[0132] Synthesis of compound 26

[0133] In air, 1,1'-bis(diphenylphosphino)ferrocene (0.05mmol), L-proline (0.1mmol), substrate 1z (0.5mmol), acetone (2.0mL), cyclopentene (1mmol) and tert-butyl hydroperoxide (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 50°C for 3h. After the reaction was completed, the product 26 was directly separated by chromatography (petroleum ether: ether V / V = 10:2) with a yield of 74%.

[0134] Embodiment 27

[0135] Synthesis of compound 27

[0136] In air, ammonium ferrous sulfate (0.1mmol), β-thiovaline (β-thionorvaline) (0.3mmol), substrate 1aa (0.5mmol), dimethyl sulfoxide (1.5mL) and water (0.5mL), cyclopentene (1mmol) and ammonium persulfate (2mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80°C for 3h. After the reaction was completed, ammonia water (0.5mL, 25%) was added and stirred for 1h. Then, 5mL of water was added and extracted with ethyl acetate (5mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was separated (petroleum ether: dichloromethane V / V=10:7) to obtain product 27 with a yield of 87%.

[0137] Embodiment 28

[0138] Synthesis of compound 28

[0139] In air, ferric fluoride (0.05 mmol), L-phenylalanine (0.1 mmol), substrate 1ab (allyl-modified BOC-L-tyrosine methyl ester) (1 mmol), acetonitrile (2 mL), 1,4-naphthoquinone (0.5 mmol) and di-tert-butyl peroxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 ° C for 3 h. After the reaction was completed, the product 28 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:1) with a yield of 55%.

[0140] 1H NMR (400MHz, CDCl3) δ8.10 (ddd, J=8.6, 5.6, 3.4Hz, 2H), 7.77 (dd, J=5.0, 3.3Hz, 2H) ,7.29–7.25(m,2H),7.23–7.17(m,1H),7.16–7.12(m,2H),6.86(d,J=4.8Hz,1H),5.0 0(d,J=7.7Hz,1H),4.58–4.43(m,2H),4.33(dd,J=11.0,5.2Hz,1H),3.74(ddd,J=31. 4,11.1,5.3Hz,2H),3.53–3.41(m,1H),3.05(d,J=6.0Hz,2H),1.42(d,J=1.7Hz,9H). 13 C NMR (100MHz, CDCl3) δ184.6,184.4,172.4,155.2,147.8,136.4,136.3,135.8,135.7,134.0,133.9,132.0,131.8 ,129.2,128.7,128.7,127.2,127.2,126.8,126.2,80.3,63.4,61.0,54.7,39.7,38.2,28.3.HRMS(ESI)calcd.for C 27 H 29 NO7Na + [M+Na] + m / z 502.1836, found 502.1839.

[0141] Embodiment 29

[0142] Synthesis of compound 29

[0143] In air, ferrous phthalocyanine (0.005mmol), L-cysteine ​​(0.02mmol), substrate 1ac (allyl-modified phenylalanine) (1mmol), N,N-diformamide (1.5mL) and water (0.5mL), 1,4-naphthoquinone (0.5mmol) and sodium persulfate (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 25°C for 24h. After the reaction was completed, ammonia water (0.5mL, 25%) was added and stirred for 1h. Then, 5mL of water was added and extracted with ethyl acetate (5mL×3). The organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was performed (petroleum ether: ethyl acetate V / V=10:6) to obtain product 29 with a yield of 49%.

[0144] 1H NMR (400MHz, CDCl3) δ8.14–8.00(m,2H),7.77–7.69(m,2H),7.00(t,J=3.9Hz,2 H),6.97(s,1H),6.82(d,J=8.7Hz,2H),6.78(s,1H),4.97(d,J=7.7Hz,1H),4.5 1(dd,J=13.0,5.2Hz,1H),4.23(ddd,J=23.9,9.5,5.9Hz,2H),4.01(t,J=5.5Hz ,1H),3.70(d,J=2.4Hz,3H),3.08–2.94(m,2H),2.93–2.76(m,1H),1.40(s,9H). 13 C NMR (100MHz, CDCl3) δ185.7,184.9,184.8,172.4,,157.4,155.1,148.5,147.6,137.2,136.5,134.0,133.9,133.8,132.1,132.1,132.1,131 .8,130.4,128.6,126.8,126.7,126.2,126.1,114.6,90.0,71.4,68.7,66.9,62.3,54.5,52.3,40.5,37.4,34.2,28.3.HRMS(ESI)calcd.forC 28 H 31 NO8Na + [M+Na] + m / z 532.1942, found 532.1947.

[0145] Embodiment 30

[0146] Synthesis of compound 30

[0147] In air, ferrous sulfate (0.05 mmol), L-cystine (0.1 mmol), substrate 1ad (allyl-modified ibuprofen) (1 mmol), ethanol (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and tert-butyl hydroperoxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60 ° C for 3 h. After the reaction was completed, the product 30 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:4) with a yield of 68%.

[0148] Embodiment 31

[0149] Synthesis of compound 31

[0150] In air, ferric oxalate (0.05 mmol), L-serine (0.1 mmol), substrate 1ae (allyl-modified diflunisal) (1 mmol), dichloromethane (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and diisopropylbenzene peroxide (1.5 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 25 ° C for 3 h. After the reaction was completed, the product 31 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:4) with a yield of 74%.

[0151] 1 H NMR(400MHz, CDCl3)δ10.61(s,1H),8.12–8.01(m,2H),7.85(s,1H),7.76–7. 70(m,2H),7.61–7.56(m,1H),7.30(td,J=8.8,6.5Hz,1H),7.03(d,J=8.7Hz, 1H),6.96(d,J=3.1Hz,1H),6.95–6.83(m,2H),4.69(ddd,J=26.8,11.1,6.2H z,2H),3.97(ddd,J=24.5,11.1,5.5Hz,2H),3.75–3.67(m,1H),2.22(s,1H). 13 C NMR (100MHz, CDCl3) δ184.5,169.8,163.37(d,J=121Hz),161.2,160.85(dd,J=11.9,9.5Hz),158.32(d,J=11.7Hz),147.9,136 .5((d,J=2.9Hz),136.4,134.0,133.9,132.0,131.7,130.94(dd,J=9.5,4.7Hz),129.89(d,J=30Hz),126.9,126.1,123.80(dd J=13.4 3.8Hz),118.0,1119,111.79(d,J=3.8Hz),111.58(d,J=3.9Hz),104.4(dd,J=26.6,25.4Hz.)HRMS(ESI)calcd.forC 26 H 18 F2O6H + [M+H] + m / z 465.1144, found 465.1146.

[0152] Embodiment 32

[0153] Synthesis of compound 32

[0154] In air, ferric nitrate (0.1mmol), L-proline (0.1mmol), substrate 1af (allyl-modified fenofibrate) (1mmol), ethanol (1.5mL) and water (0.5mL), 1,4-naphthoquinone (0.5mmol) and potassium persulfate (1.5mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 60°C for 24h. After the reaction was completed, ammonia water (0.5mL, 25%) was added and stirred for 1h. Then, 5mL of water was added and extracted with ether (5mL×3), the organic phases were combined, the solvent was removed by vacuum distillation, and then column chromatography was performed (petroleum ether: dichloromethane V / V=10:5) to obtain product 32 with a yield of 72%.

[0155] 1 H NMR (400MHz, CDCl3) δ8.07–8.00(m,1H),7.99–7.93(m,1H),7.70(d,J=5.5Hz,2H),7.67(d,J=8.7Hz,2H),7.60(d,J=8.6Hz,2H),7.44(d,J =8.2Hz,2H),6.74(d,J=7.1Hz,3H),4.46(d,J=5.8Hz,2H),3.72(ddd,J=24.1,10.9,5.8Hz,2H),3.53-3.47(m,1H),1.64(d,J=3.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ194.0,184.4,173.8,159.5,147.5,138.4,136.3,136.2,134.0,133.9,132.1,131.9, 131.6,131.2,130.2,128.6,126.8,126.1,116.7,79.3,64.0,61.3,39.9,25.5,25.4.HRMS(ESI)calcd.for C 30 H 25 ClO7Na + [M+Na] + m / z 555.1181, found 555.1185.

[0156] Embodiment 33

[0157] Synthesis of compound 33

[0158] In air, ferric chloride (0.05mmol), BOC-L-glutamic acid (0.1mmol), substrate 1ag (allyl-modified furoic acid) (1mmol), acetonitrile (1.5mL) and water (0.5mL), 1,4-naphthoquinone (0.5mmol) and potassium monopersulfate (1mmol) were added to a 25mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80℃ for 2h. After the reaction was completed, ammonia water (0.5mL, 25%) was added and stirred for 1h. Then, 5mL of water was added and extracted with ethyl acetate (5mL×3), the organic phases were combined, the solvent was evaporated under reduced pressure, and then column chromatography was separated (petroleum ether: ethyl acetate V / V=10:2) to obtain product 33 with a yield of 69%.

[0159] Embodiment 34

[0160] Synthesis of compound 34

[0161] In air, ferrous chloride (0.5 mmol), L-histidine (1.0 mmol), substrate 1ah (allyl-modified paeonol (1 mmol), dimethyl sulfoxide (4.0 mL), 1,4-naphthoquinone (0.5 mmol) and tert-butyl benzoyl peroxide (4 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 ° C for 3 h. After the reaction was completed, 5 mL of water was added, and extracted with ethyl acetate (5 mL × 3), the organic phases were combined, washed with water (5 mL × 3), and the organic phases were collected. The solvent was evaporated under reduced pressure and separated by column chromatography (petroleum ether: dichloromethane V / V = 10:4) to obtain product 34 with a yield of 77%.

[0162] 1 H NMR (400MHz, CDCl3) δ8.06(ddd,J=9.0,6.3,3.4Hz,2H),7.77(d,J=8.6Hz,1H),7.73(dd,J=5.4,3.6Hz,2H),7.02(s,1H ),6.54–6.48(m,2H),4.34(d,J=5.6Hz,2H),4.05(qd,J=11.3,4.9Hz,2H),3.85(s,3H),3.79–3.71(m,1H),2.48(s,3H). 13 C NMR (101MHz, CDCl3) δ197.4,184.8,184.6,164.6,159.7,148.6,136.6,134.0,133.9,133.4,132 .0,131.8,126.8,126.2,120.4,105.6,99.2,68.9,62.6,55.7,40.3,30.8.HRMS(ESI)calcd.for C22 H 21 O6 + [M+H] + m / z 381.1333, found 381.1327

[0163] Embodiment 35

[0164] Synthesis of compound 35

[0165] In air, ferrous acetylacetonate (0.1 mmol), N-BOC-L-leucine (0.2 mmol), substrate 1ai (allyl-modified naproxen) (1 mmol), dimethyl sulfoxide (1.5 mL) and water (0.5 mL), 1,4-naphthoquinone (0.5 mmol) and peracetic acid (1.5 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 80 ° C for 3 h. After the reaction was completed, 5 mL of water was added, and extracted with ethyl acetate (petroleum ether: ethyl acetate V / V = 10:3) (5 mL × 3), the organic phases were combined, washed with water (5 mL × 3), and the organic phases were collected. The solvent was evaporated under reduced pressure and then separated by column chromatography to obtain product 35 with a yield of 52%.

[0166] 1 H NMR(400MHz, CDCl3) δ7.98(ddd,J=10.8,6.2,3.3Hz,1H),7.95–7.88(m,1H),7.68(ddd,J=5.7,3.7,2.1Hz,2H),7.60(t,J=6.7Hz,1H) ,7.57(d,J=1.9Hz,1H),7.55(s,1H),7.31–7.26(m,1H),7.06(ddd,J=9.0,6.7,2.5Hz,1H),6.97(dd,J=12.0,2.4Hz,1H),6.64(s,1H), 6.60(s,1H),4.50(ddd,J=11.3,6.2,2.0Hz,1H),4.32(ddd,J=11.3,6.0,2.3Hz,1H),3.89(d,J=3.9Hz,3H),3.82(q,J=7.0Hz,1H),3.6 5(dt,J=10.7,5.2Hz,1H),3.56(dd,J=11.2,6.0Hz,1H),3.44(dd,J=13.0,6.1Hz,1H),2.15–1.96(m,1H),1.54(dd,J=7.1,4.2Hz,3H). 13C NMR (100MHz, CDCl3) δ184.4,184.4,184.3,184.3,174.9,174.8,157.6,157.5,147.7,14 7.5,136.1,136.0,135.1,135.1,133.8,133.7,133.7,133.7,133.6,133.6,131.9,131. 6,131.5,129.2,129.2,128.7,128.7,127.4,126.7,126.0,126.0,119.1,119.1,105.5, 105.5,62.8,62.6,61.4,61.3,55.3,55.3,45.4,45.4,40.1,40.1.HRMS(ESI)calcd.for C27H25O6+[M+H]+m / z 445.1646, found 445.1640.

[0167] Embodiment 36

[0168] Synthesis of compound 36

[0169] In air, iron acetylacetonate (0.05 mmol), BOC-glycine-glycine-glycine (0.1 mmol), substrate 1aj (allyl-modified indomethacin) (1 mmol), N,N-diethylamide (1.0 mL) and water (0.1 mL), 1,4-naphthoquinone (0.5 mmol) and tert-butyl hydroperoxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 100 ° C for 3 h. After the reaction was completed, ammonia water (0.5 mL, 25%) was added and stirred for 1 h. Then, 5 mL of water was added, and extracted with ethyl acetate (5 mL×3), the organic phases were combined, the solvent was removed by vacuum distillation, and then column chromatography was separated (petroleum ether: ethyl acetate V / V=10:4) to obtain product 36 with a yield of 59%.

[0170] 1 H NMR (400MHz, CDCl3) δ8.07–8.00(m,1H),7.99–7.91(m,1H),7.76–7.62(m,4H),7.48(d,J=8.2Hz,2H),6.84(d,J=1.5Hz,1H),6.75(d,J=9.0Hz,1H), 6.58(s,1H),6.51(d,J=8.8Hz,1H),4.45(d,J=5.7Hz,1H),3.75(s,3H),3 .68(dd,J=11.1,5.9Hz,1H),3.63(s,2H),3.52–3.43(m,1H),2.32(s,3H). 13C NMR (100MHz, CDCl3) δ184.3,184.2,170.9,168.2,155.8,147.6,139.2,135.9,135.9,133.8,133.8,133.7,131.8,131.5,131 .1,130.6,130.2,129.1,126.7,126.1,115.1,112.1,111.7,100.9,63.1,61.4,55.6,40.1,30.4,13.3.HRMS(ESI)calcd.for C 32 H 27 ClNO7 + [M+H] + m / z 572.1471, found 572.1471.

[0171] Embodiment 37

[0172] Synthesis of compound 37

[0173] In air, iron (III) perchlorate hydrate (0.05 mmol), L-homocystine (0.1 mmol), substrate 1ak (drug molecule quinidine) (1 mmol), dichloromethane (2.0 mL), 1,4-naphthoquinone (0.5 mmol) and hydrogen peroxide (1 mmol) were added to a 25 mL reaction bottle in sequence. After mixing evenly at room temperature, the reaction mixture was stirred at 40 ° C for 3 h. After the reaction was completed, the product 37 was directly separated by chromatography (petroleum ether: ethyl acetate V / V = 10:2) with a yield of 67%.

[0174] The raw materials and product structural formulas of Examples 1 to 37 and the corresponding experimental results are shown in Table 1 below:

[0175] Table 1

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] Embodiment 39

[0183] The method of Example 39 is the same as that of Example 1, except that the molar ratio of the quinone compound, the olefin compound, the peroxide, the amino acid derivative, and the iron catalyst is 1:0.5:2:0.002:0.001.

[0184] Embodiment 40

[0185] The method of Example 40 is the same as that of Example 1, except that the molar ratio of the quinone compound, the olefin compound, the peroxide, the amino acid derivative, and the iron catalyst is 1:10:50:20:10.

[0186] Embodiment 41

[0187] The method of Example 41 is the same as that of Example 1, except that the solvent is all water and the total volume remains unchanged.

[0188] Embodiment 42

[0189] The method of Example 42 is the same as that of Example 1, except that the volume ratio of the solvent (dimethyl sulfoxide and water) is 1:0.1.

[0190] Embodiment 43

[0191] The method of Example 43 is the same as that of Example 1, except that the volume ratio of the solvent (ethanol and water) is 1:5.

[0192] Embodiment 44

[0193] The method of Example 44 is the same as that of Example 1, except that the reaction temperature is 25°C and the reaction time is 24 hours.

[0194] Embodiment 45

[0195] The method of Example 45 is the same as that of Example 1, except that the reaction temperature is 150° C. and the reaction time is 0.25 hours.

[0196] Comparative Example 1

[0197] The method of Comparative Example 1 is the same as that of Example 1, except that no iron catalyst is added and the yield of the target product is 0.

[0198] Comparative Example 2

[0199] The method of Comparative Example 2 is the same as that of Example 1, except that: without adding amino acid ligands, the reaction yield is significantly reduced, and the yield is less than 40%.

[0200] Comparative Example 3

[0201] Comparative Example 3 is the same as Example 1, except that no oxidant is added and the yield of the target product is less than 5%.

[0202] Comparative Example 4

[0203] Comparative Example 4 is the same as Example 1, except that the ratio of the olefin compound raw material is increased from the current two equivalents to three equivalents, and the yield does not change significantly.

[0204] Comparative Example 5

[0205] Comparative Example 5 is the same as the method of Example 1, except that: using non-amino acid ligand 1,10-phenanthroline, the yield is less than 10%. In addition, using other phosphorus-containing ligands, such as triphenylphosphine, tris(pentafluorophenyl)phosphine, bis(triphenylphosphine)ammonium chloride, the effect is not good, and the yield is very low.

[0206] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. The various iron catalysts in the present invention can theoretically coordinate with amino acid ligands to form highly active iron catalyst species, which is conducive to the smooth progress of the reaction; amino acid ligands are promoters for the carbon hydroxylation reaction of olefins, and the effect of their coordination with iron is utilized. The various amino acids and their derivatives given in theory have coordination functions and should be able to achieve similar effects; various peroxides are oxidants; what occurs on the aromatic substrate is the activation of carbon-hydrogen bonds, and the various substituents on the aromatic ring affect the size of the electron cloud density in the ring and the size of the steric hindrance during the reaction, that is, the modification of the substituent only affects the reaction to a certain extent, and does not play a decisive role in the occurrence of the reaction. Any technician familiar with this profession will not find it difficult to understand that without departing from the scope of the technical solution of the present invention, when changes or modifications can be made to obtain corresponding embodiments, for example, the substituents can be replaced, changed or modified within the scope of the present invention, and the method of the present invention can be realized. Any modification, alteration or equivalent changes made to the above embodiments according to the present invention without departing from the purpose of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method for the iron-catalyzed quinone hydroxylation of olefins, characterized in that: The method comprises the following steps: in a solvent, using a quinone compound as a substrate, an olefin compound as a hydroxylation substrate, a peroxide as an oxidant, iron as a catalyst, and an amino acid or its derivative as a ligand, catalyzing the olefin C(sp 2 )-H bond dehydrogenation coupling with quinone compounds to generate alcoholized quinone compounds; The general reaction formula is as follows: In the formula: R1 represents the substituent on the aromatic group in the aromatic hydrocarbon of the quinone compound, and R1 is an electron-donating group or an electron-withdrawing group; R2 is the substituent on the 2nd position of the quinone compound, and R2 is an electron-donating group or an electron-withdrawing group; R is hydrogen, alkyl or carbonyl, and R' is hydrogen, alkyl, carbonyl, halogen, phenyl, benzyl, ester or hydroxyl.

2. The method for the iron-catalyzed quinone hydroxylation of olefins according to claim 1, characterized in that: R1 represents hydrogen, C1-C5 alkyl, hydroxyl, methoxy, and R2 represents hydrogen, C1-C5 alkyl, amino, hydroxyl, ester, methoxy, ethoxy, isopropyl or halogen.

3. The method for the iron-catalyzed quinone hydroxylation of olefins according to claim 1, characterized in that: R represents C1-C5 alkyl, carbonyl or hydrogen, and R' represents hydrogen, C1-C5 alkyl, halogen, phenyl, benzyl, ester group, hydroxyl or tert-butyloxycarbonyl.

4. The method for the iron-catalyzed quinone hydroxylation of olefins according to claim 1, characterized in that: R is preferably hydrogen, methyl, ethyl, isopropyl; R' is preferably tert-butyloxycarbonyl, ester, hydroxyl, C1-C3 alkyl.

5. The method for the iron-catalyzed quinone hydroxylation of olefins according to any one of claims 1 to 4, characterized in that: The iron is selected from any one of ferrous trifluoromethanesulfonate, ferrous trifluoromethanesulfonate, ferrous chloride, ferrous acetylacetonate, ferrous acetylacetonate, ferrous 2,2,6,6-tetramethyl-3,5-heptanedione ferrous, ferrous 2,2,6,6-tetramethyl-3,5-heptanedione, ferrous 1,3-diphenylpropanedione, ferrous 1,3-diphenylpropanedione, ferrous benzoylacetonate, ferrous benzoylacetonate, ferrous ferrocyanide, ferrous ferrocyanide, ferrous acetate, ferrous sulfate, ammonium ferrous sulfate, ferrous sulfate, ferrous oxalate, ferrous oxalate, ferrous fluoride, ferrous fluoride, ferrous bromide, ferrous bromide, ferrous iodide, ferric chloride, iron (III) perchlorate hydrate, 1,1'-bis(diphenylphosphino)ferrocene, ferrous phthalocyanine, ferric nitrate, ferric oxide or ferric oxide.

6. The method for the iron-catalyzed quinone hydroxylation of olefins according to any one of claims 1 to 4, characterized in that: The ligand is selected from any one of S-acetylaminomethyl-N-tert-butyloxycarbonyl-L-cysteine, N-acetyl-L-cysteine, N,N'-bis(tert-butyloxycarbonyl)-L-cystine, β-thiovaline, L-serine, D-cystine, aspartic acid, D-arginine, isoserine, L-threonine, L-tyrosine, BOC-L-proline, BOC-glycine-glycine-glycine, BOC-D-phenylalanine, L-cysteine, D-serine, D-proline, D-valine, L-proline, L-phenylalanine, N-BOC-N'-trityl-L-histidine, L-tryptophan, N-BOC-L-leucine, L-histidine, BOC-L-glutamate, L-cystine, or L-homocysteine.

7. The method for the iron-catalyzed quinone hydroxylation of olefins according to any one of claims 1 to 4, characterized in that: The oxidant is selected from any one of potassium persulfate, ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide, hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, benzoyl peroxide, tert-butyl benzoyl peroxide, di-tert-butyl peroxide, potassium monopersulfate, diisopropylbenzene peroxide, 2-methyl ethyl peroxide or bis(trimethylsilyl)peroxide.

8. The method for the iron-catalyzed quinone hydroxylation of olefins according to any one of claims 1 to 4, characterized in that: The solvent is an organic solvent, water or an aqueous solution of an organic solvent. The organic solvent is selected from any one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1,3-propylene glycol, glycerol, n-butanol, isobutanol, tert-butanol, trifluoroethanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, tert-amyl alcohol, 4-methyl-2-pentanol, isopentanol, 2-pentanol, 3-pentanol, cyclopentanol, n-pentanol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, acetone, dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide, N,N-diformamide, N,N-diacetamide, ethyl acetate, 1,4-dioxane or tetrahydrofuran. When the solvent is an aqueous solution of an organic solvent, the volume ratio of the organic solvent to water is 1:(0.1-5).

9. The method for the iron-catalyzed quinone hydroxylation of olefins according to any one of claims 1 to 4, characterized in that: The olefin compounds include electron-withdrawing, electron-donating internal olefin compounds or electron-withdrawing, electron-donating terminal olefin compounds.

10. The method for the iron-catalyzed quinone hydroxylation of olefins according to any one of claims 1 to 4, characterized in that: The molar ratio of the quinone compound, olefin compound, peroxide, amino acid or its derivative, and iron catalyst is 1:(0.5-50):(2-50):(0.002-20):(0.001-10); the reaction temperature is 25-150° C. and the reaction time is 0.25-24 hours.

Images