Synthesis and Application of a Class of Innovative Haloperoxidase Biomimetic Catalysts

Abstract

The present invention provides a green method for the synthesis and application of an innovative haloperoxidase biomimetic catalyst based on the Fenton reaction, belonging to the field of green organic chemistry. This method uses an iron complex haloperoxidase obtained by chelating FeBr3 / FeBr2 with 2,2′:6′,2″-terpyridine organic ligands containing different substituents as the catalyst, H2O2 as the only oxidant, H2O as a byproduct, and inexpensive and readily available magnesium bromide hydrate as the bromine source. Under neutral and room temperature conditions, the synthesis of various organic molecules can be completed within a short time, such as bromination of phenol red, deprotection of thioacetal, oxidation of indole, oxidation of thioether, Achmatowicz rearrangement, etc. The present invention applies the Fenton reaction to the construction of a haloperoxidase biomimetic system for the first time, further improving the problem of low catalytic efficiency on the basis of the selective oxidation of HO·. It has the characteristics of high catalytic activity, good stability, mild reaction conditions, and short synthetic route, and is a very green, environmentally friendly, efficient, and widely applicable catalytic synthesis method with good application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical fields of green chemistry and organic synthesis, and particularly relates to an iron complex haloperoxidase biomimetic catalyst in which FeBr3 chelates an organic ligand with 2,2':6',2''-terpyridine as the core, and a green method for efficiently catalyzing the synthesis of a large class of organic molecules based on the Fenton reaction. Background Art

[0002] Halogenation reactions are a class of extremely important organic synthesis reactions. Traditional halogenation reactions need to be improved due to problems such as the use of toxic and harmful reagents and lack of selectivity in the reactions. For example, when using traditional bromination reagents (such as Br2, BrCl, NBS, etc.) to prepare bromides, there are problems such as environmental pollution, unfriendly operation, and low bromine atom utilization rate. The outstanding advantage of enzyme-catalyzed halogenation reactions is that under normal temperature and pressure, mild-source halogens can be used for efficient catalytic reactions, but the enzyme activity is unstable, the price is expensive, it is not easy to obtain, it is difficult to scale up, and a large amount of buffer solution is required. The haloperoxidase method is a very green Br - in-situ oxidation method. This enzyme uses H2O2 as a green oxidant and catalyzes the halogenation of various biosynthetic precursors through the enzyme active center. Developing a green, safe, and efficient Br - in-situ oxidation strategy for the synthesis of a large class of organic molecules is of far-reaching significance.

[0003] HO·, as a strong oxidizing free radical, can oxidize Br - to Br + , and HO· is an active oxidizing substance generated by the Fenton reaction and can be decomposed from H2O2 under the catalysis of Fe 2+ / Fe 3+ . Therefore, applying the Fenton reaction to the construction of a haloperoxidase biomimetic system to achieve Br - in-situ oxidation, the generated Br + can not only be used for bromination reactions but also participate in a series of oxidation and rearrangement reactions of organic molecules (such as hydroxyl oxidation, thioacetal deprotection, indole oxidation, thioether and thiol oxidation, Achmatowicz rearrangement, etc.). This is completely different from the strategies of currently commonly relied-on heme-dependent haloperoxidases to form high-valent Fe=O complexes and vanadium-dependent haloperoxidases to form vanadium peroxo active intermediates to oxidize Br - .

[0004] Currently, the Fenton reaction mainly focuses on pollutant degradation. The strong oxidizing free radical HO· generated can degrade organic pollutants into environmentally harmless small molecules (such as carbon dioxide and water). However, in organic synthesis, there are defects such as over-oxidation, complex products, and low yields. Moreover, Fenton metals are prone to form "iron sludge" precipitation, resulting in low catalytic efficiency. Developing a new haloperoxidase biomimetic catalytic system based on the Fenton reaction for the efficient and selective catalytic synthesis of a large class of organic molecules is of great significance.

[0005] In summary, in this study, a specific organic ligand (such as 2,2′:6′,2″-terpyridine) was introduced and complexed with FeBr3 / FeBr2 to prepare a coordination complex containing Fe-Br bonds, forming a haloperoxidase biomimetic system for the efficient catalytic synthesis of a large class of organic molecules. The bromoperoxidase activity of this iron complex was evaluated by the oxidation of phenol red to bromophenol blue, and a specific fluorescence probe for intramolecular S=N cyclization initiated by HOBr was synthesized to detect the generation of HOBr. The strong oxidizing free radical HO· generated by the decomposition of H2O2 catalyzed by Fenton metal (Fe) can be promptly captured by the adjacent Br - (Fe-Br) to generate a mild oxidant Br + , avoiding side reactions caused by the non-selective oxidation of excessive HO·. At the same time, as a homogeneous catalyst, the organic ligand increases the solubility of the Fenton catalyst and catalytic intermediate states in the organic phase, preventing the catalytic active center (Fe 2+ / 3+ ) from forming "iron sludge" precipitation and precipitating out of the reaction system, thus facilitating the improvement of the turnover number and catalytic efficiency of the catalyst to solve the problems of poor oxidation selectivity and low catalytic efficiency of the Fenton reaction in organic synthesis. The haloperoxidase biomimetic catalyst in this study mimics the naturally occurring haloperoxidase and is of great significance for the green and efficient synthesis of various biosynthetic precursors and important organic compounds used in catalyzing halogenation.

[0006] Therefore, developing a green, efficient, and generally applicable innovative haloperoxidase biomimetic catalyst for the synthesis of natural biosynthetic precursors and a large class of important organic molecules is of great significance. Summary of the Invention

[0007] The object of the present invention is to develop an innovative haloperoxidase biomimetic catalyst based on the Fenton reaction and a green and general method for the efficient catalytic synthesis of various organic molecules, which is simple, efficient, environmentally friendly, easy to operate, and has a wide application range.

[0008] The technical solution adopted by the present invention is as follows:

[0009] Under neutral and room temperature conditions, a halogen peroxidase of an iron complex chelating 2,2':6',2''-terpyridine organic ligands with different substituents using FeBr3 / FeBr2 as a catalyst, H2O2 as the sole oxidant, and inexpensive and readily available magnesium bromide hexahydrate as the bromine source, the synthesis of various organic molecules is completed within a short time. Such as the halogenation reaction of organic molecules, the conversion of 1,3-dithiane derivatives into carbonyl compounds, the preparation of sulfoxide compounds, the cyclization of sulfur-nitrogen double bonds, the oxidative rearrangement of indole derivatives, the Achmatowicz rearrangement, etc.

[0010] The catalyst used in the reaction is a halogen peroxidase biomimetic catalyst, and the molar ratio of the catalyst to the raw material organic molecule is 0.01-0.2:1. The structure of the catalyst is shown in Formula I:

[0011]

[0012] Among them, R1, R2, and R3 can be common groups such as hydrogen atom, carboxyl group, tert-butyl group, methoxy group, phenyl group, bromophenyl group, halogen atom, etc.

[0013] The oxidant used in the reaction is hydrogen peroxide, and the molar ratio of hydrogen peroxide to the raw material organic molecule is 1-4:1.

[0014] The solvent used in the reaction can be ethanol, acetonitrile, tetrahydrofuran, etc., and their mixed solvents with water in different proportions.

[0015] The reaction substrates are organic sulfides with different functional groups, nitrogen-containing organic sulfides, 1,3-dithiane derivatives, substituted benzene compounds, furfuryl alcohol, indole derivatives, phenol red, etc. The structures of the reaction substrates are shown in Formulas II-VIII:

[0016]

[0017] Among them, R, R1, R2, R3, and R4 can be different functional groups such as hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, ester group, alicyclic hydrocarbon, etc., or different substituents such as furan, pyridine, thiophene, pyrrole, and other heterocycles, and can also be common protecting groups such as Ac, TBS, THP, Bn, Boc, and TIPS, etc.

[0018] The preferred reaction time of the reaction is 15 min, and the reaction temperature is room temperature.

[0019] The treatment method of the reaction is that after the reaction is completed, it is quenched with a Na2S2O3 solution and extracted with an organic solvent (such as ethyl acetate, dichloromethane). The organic phase is collected, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the product.

[0020] The beneficial effects of the present invention:

[0021] The present invention has the following advantages and effects compared with the prior art:

[0022] For the first time, the present invention applies the Fenton reaction to the construction of a haloperoxidase biomimetic system, realizes the simple synthesis of an iron complex haloperoxidase biomimetic catalyst, uses H2O2 as the sole oxidant, and is applied to the efficient synthesis of a large class of organic molecules under neutral and room temperature conditions. The bromoperoxidase activity of the iron complex was evaluated by the oxidation of phenol red to bromophenol blue. By introducing an organic ligand, the present invention forms a homogeneous catalyst, increases the solubility of the Fenton catalyst and the catalytic intermediate state in the organic phase, and avoids the precipitation of the catalytic active center (Fe 2+ / 3+ ) as "iron mud" from the reaction system, thereby facilitating the improvement of the turnover number and catalytic efficiency of the catalyst to solve the problems of poor oxidation selectivity and low catalytic efficiency existing in the Fenton reaction in organic synthesis. Compared with the existing organic molecule halogenation oxidation methods, this method has the characteristics of low cost, fast reaction, high yield, wide substrate applicability, mild reaction conditions, simple route, easy operation, environmental friendliness, etc., and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 and Figure 2 are the 1 H-NMR and 13 C-NMR spectra of Example 1

[0024] Figure 3 are the 1 H-NMR spectra of Example 2

[0025] Figure 4 and Figure 5 are the 1 H-NMR and 13 C-NMR spectra of Example 3

[0026] Figure 6 and Figure 7 are the 1 H-NMR and 13 C-NMR spectra of Example 4

[0027] Figure 8 and Figure 9 are the 1 H-NMR and 13 C-NMR spectra of Example 5

[0028] Figure 10 and Figure 11 are the 1 H-NMR and 13 C-NMR spectra of Example 6

[0029] Figure 12 and Figure 13 are the 1 H-NMR and 13 C-NMR spectra

[0030] Figure 14 and Figure 15 are the 1 H-NMR and 13 C-NMR spectra

[0031] Figure 16 and Figure 17 are the 1 H-NMR and 13 C-NMR spectra

[0032] Figure 18 and Figure 19 are the 1 H-NMR and 13 C-NMR spectra

[0033] Figure 20 and Figure 21 are the 1 H-NMR and 13 C-NMR spectra

[0034] Figure 22 and Figure 23 are the 1 H-NMR and 13 C-NMR spectra

[0035] Figure 24 and Figure 25 are the 1 H-NMR and 13 C-NMR spectra

[0036] Figure 26 and Figure 27 are the 1 H-NMR and 13 C-NMR spectra

[0037] Figure 28 and Figure 29 are the 1 H-NMR and 13 C-NMR spectra

[0038] Figure 30 and Figure 31 are the 1 H-NMR and 13 C-NMR spectra Detailed implementation mode

[0039] The present invention will be described in detail with specific implementation examples below, but the protection scope of the present invention is not limited thereto.

[0040] In the following examples 1 1H-NMR and 13 13C-NMR spectra were measured under room temperature conditions, recorded on a 400 MHz spectrometer, 1 1H was 400 MHz, 13 13C was 100 MHz, and the spectrometer was from Bruker Corporation.

[0041] Example 1

[0042]

[0043] 1a (10 mmol, 2.33 g), FeBr3 (11 mmol, 3.25 g), and 50 ml of ACN were successively added to a 100 ml round-bottom flask, stirred for 1 h. After the reaction was completed, the volume was reduced by rotary evaporation, ethyl acetate was added, and filtration was carried out to obtain the target product 1b (yield: 98%). The characterization data of this compound are as follows: 1 1H NMR (400 MHz, CDCl3) δ 9.37 - 9.20 (m, 2H), 8.89 - 8.78 (m, 3H), 8.00 (t, J = 7.7 Hz, 2H), 7.22 - 7.08 (m, 4H). 13 13C NMR (100 MHz, CDCl3) δ 159.62, 157.56, 152.65, 138.81, 138.13, 127.64, 124.04, 123.93.

[0044] Example 2

[0045]

[0046] MgBr2·6H2O (98 mmol, 19.81 g) and 28 ml of ACN / H2O (3 / 1) were added to a 100 ml round-bottom flask. 2a (2.8 mmol, 1 g) and the haloperoxidase biomimetic catalyst 1b (0.56 mmol, 0.30 g) were added. After stirring at room temperature for 15 min, an aqueous H2O2 solution (30 wt%, 84 mmol, 8.43 ml) was added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the solvent was removed by rotary evaporation, and the target product 2b was purified by column chromatography (yield: 70%). The characterization data of this compound are as follows: 11H NMR (400 MHz, DMSO-d6) δ 7.93 (d, J = 7.7 Hz, 1H), 7.78 - 7.41 (m, 6H), 7.14 (s, 1H). HRMS (ESI+) (m / z) calcd. for C 19 H 11 Br4O5S [M+H] + 670.7014; found 670.7026.

[0047] Example 3

[0048]

[0049] MgBr2·6H2O (2.5 mmol, 0.51 g) and 25 ml of EtOH / H2O (3 / 1) were added to a 100 ml round-bottom flask. 3a (5 mmol, 1.08 g) was added and stirred evenly. To the mixture were successively added the haloperoxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and an aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml), and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with a Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 3b (yield: 75%). The characterization data of this compound are as follows: 1 1H-NMR (400 MHz, CDCl3) δ: 7.96 (d, J = 8.0 Hz, 1H), 7.89 (dd, J = 7.9, 1.5 Hz, 1H), 7.60 - 7.55 (m, 1H), 7.42 - 7.40 (m, 2H), 7.32 - 7.27 (m, 1H), 7.22 (dd, J = 8.1, 1.4 Hz, 1H), 6.99 - 6.94 (m, 1H), 2.33 (s, 3H). 13 13C-NMR (100 MHz, CDCl3) δ: 148.6, 132.5, 131.8, 130.4, 127.5, 125.8, 124.7, 124.5, 124.2, 123.5, 120.8, 119.7, 32.0.

[0050] Example 4

[0051]

[0052] MgBr2·6H2O (2.5 mmol, 0.51 g) and 25 ml of EtOH / H2O (3 / 1) were added to a 100 ml round-bottom flask. 4a (5 mmol, 1.15 g) was added and stirred evenly. Subsequently, the halogen peroxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and an aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were added to the mixture, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with a Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 4b (yield: 70%). The characterization data of this compound are as follows: 1 1H-NMR (400 MHz, CDCl3) δ: 7.92 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.58 - 7.53 (m, 1H), 7.41 - 7.34 (m, 2H), 7.03 (s, 1H), 6.80 (d, J = 8.0 Hz, 1H), 2.34 (s, 3H), 2.32 (s, 3H). 13 13C-NMR (100 MHz, CDCl3) δ: 148.7, 140.7, 132.6, 131.7, 127.1, 125.9, 124.4, 124.3, 124.0, 123.1, 121.0, 118.2, 32.1, 21.5.

[0053] Example 5

[0054]

[0055] 5a (5 mmol, 0.62 g) and 25 ml of THF were successively added to a 100 ml round-bottom flask and stirred evenly. Subsequently, the halogen peroxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and an aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were added to the mixture of the two, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with a Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with ethyl acetate (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 5b (yield: 97%). The characterization data of this compound are as follows: 1 1H-NMR (400 MHz, CDCl3) δ: 7.65 - 7.62 (m, 2H), 7.52 - 7.49 (m, 3H), 2.70 (s, 3H). 13 13C-NMR (100 MHz, CDCl3) δ: 145.8, 131.0, 129.4, 123.5, 44.0.

[0056] Example 6

[0057]

[0058] 6a (5 mmol, 0.69 g) and 25 ml of THF were successively added to a 100 ml round-bottom flask, stirred evenly. To the mixture of the two, haloperoxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with ethyl acetate (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 6b (yield: 85%). The characterization data of this compound are as follows: 1 1H-NMR (400 MHz, CDCl3) δ: 7.53 (d, J = 8.2 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 2.68 (s, 3H), 2.40 (s, 3H). 13 13C-NMR (100 MHz, CDCl3) δ: 142.5, 141.5, 130.0, 123.6, 44.0, 21.4.

[0059] Example 7

[0060]

[0061] 7a (5 mmol, 0.49 g) and 25 ml of THF / H2O (3 / 1) were successively added to a 100 ml round-bottom flask, stirred evenly. To the mixture of the two, haloperoxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with ethyl acetate (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 7b (yield: 70%). The characterization data of this compound are as follows: 1 1H NMR (400 MHz, CDCl3) δ 6.95 (dd, J = 10.4, 3.0 Hz, 1H), 6.16 (d, J = 10.4 Hz, 1H), 5.63 (d, J = 3.0 Hz, 1H), 4.57 (d, J = 16.9 Hz, 1H), 4.13 (d, J = 16.9 Hz, 1H). 1313C NMR (100 MHz, CDCl3) δ 194.75, 145.93, 128.04, 88.35, 66.74.

[0062] Example 8

[0063]

[0064]

[0065] 8a (5 mmol, 0.66 g) and THF / H2O (3 / 1) 25 ml were successively added into a 100 ml round-bottom flask, stirred evenly. To the mixture, bromoperoxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 8b (yield: 60%). The characterization data of this compound are as follows: 1 1H NMR (400 MHz, CDCl3) δ 9.28 (s, 1H), 7.24 - 7.17 (m, 2H), 7.03 (td, J = 7.6, 2.5 Hz, 1H), 6.94 (dd, J = 8.4, 2.3 Hz, 1H), 3.51 - 3.43 (m, 1H), 1.50 (d, J = 7.7 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 181.91, 141.47, 131.37, 128.00, 123.84, 122.45, 110.02, 41.26, 15.33.

[0066] Example 9

[0067]

[0068] 9a (5 mmol, 0.99 g) and ACN 25 ml were successively added into a 100 ml round-bottom flask, stirred evenly. To the mixture, iron complex bromoperoxidase catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL). The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 9b (yield: 65%). The characterization data of this compound are as follows: 11H NMR (400 MHz, CDCl3) δ 7.30 (dd, J = 8.7, 7.4 Hz, 2H), 7.00 - 6.91 (m, 3H), 4.10 - 4.07 (m, 2H), 3.98 - 3.95 (m, 2H), 2.19 - 2.13 (m, 1H). 13 13C NMR (100 MHz, CDCl3) δ 158.40, 129.34, 120.94, 114.36, 68.88, 61.29.

[0069] Example 10

[0070]

[0071] 10a (5 mmol, 1.05 g) and 25 ml of ACN were successively added to a 100 ml round-bottom flask and stirred evenly. To the mixture of the two, the halogen peroxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and an aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with a Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 10b (yield: 75%). The characterization data of this compound are as follows: 1 1H NMR (400 MHz, CDCl3) δ 7.99 - 7.93 (m, 2H), 7.59 - 7.53 (m, 1H), 7.46 (t, J = 7.6 Hz, 2H), 2.60 (s, 3H). 13 13C NMR (100 MHz, CDCl3) δ 198.28, 137.26, 133.23, 128.69, 128.43, 26.73.

[0072] Example 11

[0073]

[0074] 11a (4 mmol, 1.10 g) and THF / H2O (3 / 1) 20 ml were successively added into a 100 ml round-bottom flask, stirred evenly. To the mixture, halogen peroxidase biomimetic catalyst 1b (0.4 mmol, 0.21 g) and aqueous H2O2 solution (30 wt%, 8 mmol, 0.80 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 40 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 11b (yield: 87%). The characterization data of this compound are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.84 - 7.79 (m, 2H), 7.62 - 7.58 (m, 2H), 2.58 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 197.14, 135.97, 132.03, 129.97, 128.44, 26.67.

[0075] Example 12

[0076]

[0077] 12a (5 mmol, 1.25 g) and ACN 25 ml were successively added into a 100 ml round-bottom flask, stirred evenly. To the mixture, halogen peroxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 12b (yield: 80%). The characterization data of this compound are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.40 (s, 1H), 7.86 (d, J = 8.7 Hz, 1H), 7.47 (s, 1H), 7.37 (d, J = 7.3 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 188.64, 141.23, 138.66, 131.05, 130.58, 130.44, 128.09.

[0078] Example 13

[0079]

[0080] 13a (5 mmol, 1.37 g) and 25 ml of ACN were successively added into a 100 ml round-bottom flask, stirred evenly. To the mixture of the two, the halogenoperoxidase biomimetic catalyst 1b (0.5 mmol, 0.26 g) and the aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with a Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 13b (yield: 85%). The characterization data of this compound are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.39 (s, 1H), 8.01 (d, J = 9.4 Hz, 1H), 7.83 (d, J = 9.0 Hz, 1H), 7.75 (d, J = 8.6 Hz, 1H), 7.19 (d, J = 9.1 Hz, 1H), 7.14 (s, 1H), 3.93 (s, 3H), 3.10 (q, J = 7.3 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 200.66, 159.73, 137.27, 132.42, 131.18, 129.48, 127.95, 127.16, 124.74, 119.75, 105.80, 55.50, 31.77, 8.58.

[0081] Example 14

[0082]

[0083] 14a (5 mmol, 1.26 g) and 25 ml of ACN were successively added into a 100 ml round-bottom flask, stirred evenly. To the mixture of the two, the iron complex halogenoperoxidase catalyst 1b (0.5 mmol, 0.26 g) and the aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with a Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 14b (yield: 80%). The characterization data of this compound are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.96 (s, 1H), 7.77 (d, J = 8.2 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). 1313C NMR (100 MHz, CDCl3) δ 192.11, 145.66, 134.32, 129.96, 129.82, 21.99.

[0084] Example 15

[0085]

[0086] 15a (5 mmol, 1.57 g) and 25 ml of EtOH were successively added to a 100 ml round-bottom flask and stirred evenly. To the mixture of the two, iron complex haloperoxidase catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 15b (yield: 70%). The characterization data of this compound are as follows: 1 1H NMR (400 MHz, CDCl3) δ 11.48 (s, 1H), 8.95 (d, J = 9.0 Hz, 2H), 8.62 (s, 1H), 8.01 (d, J = 8.3 Hz, 2H), 7.66 (t, J = 7.9 Hz, 2H), 7.52 (t, J = 7.6 Hz, 2H). 13 13C NMR (100 MHz, CDCl3) δ 193.08, 135.32, 132.20, 131.13, 129.38, 129.21, 125.77, 124.75, 123.62.

[0087] Example 16

[0088]

[0089] 16a (5 mmol, 1.83 g) and 25 ml of ACN were successively added to a 100 ml round-bottom flask and stirred evenly. To the mixture of the two, iron complex haloperoxidase catalyst 1b (0.5 mmol, 0.26 g) and aqueous H2O2 solution (30 wt%, 10 mmol, 1.00 ml) were successively added, and the reaction was stirred at room temperature for 15 min. After the reaction was completed, the reaction was quenched with Na2S2O3 solution (0.1 M, 50 mL). The aqueous phase was extracted with dichloromethane (2 x 50 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 16b (yield: 65%). The characterization data of this compound are as follows: 11H NMR (400 MHz, CDCl3) δ 9.87 (s, 1H), 7.83 (d, J = 8.9 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.88 (s, 3H). 13 13C NMR (100 MHz, CDCl3) δ 190.92, 164.72, 132.09, 130.08, 114.42, 55.69.

Claims

1. Application of a haloperoxidase biomimetic catalyst based on Fenton reaction, characterized in that: Under neutral and room temperature conditions, with various organic molecules as substrates, a halogen peroxidase chelating FeBr3 / FeBr2 with an organic ligand based on 2,2′:6′,2″-terpyridine as a homogeneous catalyst, and H2O2 as the sole oxidant, the bromination of phenol red, the carbonylation of 1,3-dithiane derivatives, the preparation of sulfoxide compounds, the cyclization of sulfur-nitrogen double bonds, the oxidative rearrangement of indole derivatives, and the oxidation reaction of furfuryl alcohol are completed within a short time; the substrates are organic sulfides, furfuryl alcohol, 1,3-dithiane derivatives, indole derivatives or phenol red with different functional groups; the molar ratio of the catalyst to the organic molecule is 0.01-0.2:1; the molar ratio of H2O2 to the organic molecule is 1-4:1; the reaction is carried out in a solvent, and the solvents used are ethanol, acetonitrile or tetrahydrofuran, and their mixed solvents with different proportions of water, and the ratio of the amount of the organic molecule to the solvent is 1 mmol / 5-16 ml.

2. The application according to claim 1, characterized in that: The reaction time is 15 min.

3. The application according to claim 1, characterized in that: During specific operation, the raw material organic molecule is added to an appropriate amount of solvent and stirred evenly, then the halogen peroxidase biomimetic catalyst and the H2O2 aqueous solution are added, and the reaction mixture is stirred at room temperature for 15 min to complete the halogenation of the organic molecule, the carbonylation of 1,3-dithiane derivatives, the preparation of sulfoxide compounds, the cyclization of sulfur-nitrogen double bonds, the oxidative rearrangement of indole derivatives, and the oxidation reaction of furfuryl alcohol.

4. The application according to claim 3, wherein: The treatment method of the said reaction is that after the reaction is completed, it is quenched with a diluted Na2S2O3 solution, extracted with an organic solvent, the organic phase is collected, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the product; the above-mentioned organic solvent is dichloromethane or ethyl acetate.

Images