Fluorine sulfonyl salt as well as preparation method and application thereof

Abstract

The invention relates to a fluorosulfonyl salt and a preparation method and application thereof, the chemical formula of the fluorosulfonyl salt is R + SO2F-, M (SO2F) Z or LxM (SO2F) Z. The preparation method comprises the following steps: taking fluoride and a sulfur dioxide source as raw materials to react in a solvent, and filtering after the reaction is finished to obtain an M + SO2F-solution; adding RX into the solution, stirring at room temperature, washing and extracting after the reaction is finished, collecting an organic phase, adding anhydrous sodium sulfite, drying, and removing the solvent in vacuum to obtain R < + > SO2F <->; or placing the M + SO2F <-> solution in a low-temperature environment, dropwise adding a diethyl ether solution of the ligand L into the filtrate, standing at low temperature after the reaction is finished, separating out a solid, and washing to obtain (LxM (SO2F) Z). Compared with the prior art, the method has the advantages of cheap and easily available initial raw materials, mild reaction conditions, simple post-treatment, high yield and wide application prospect; the fluorosulfonyl salt has nucleophilicity and can be used as a nucleophilic fluorosulfonylation reagent to introduce fluorosulfonyl into molecules.

Description

Technical Field

[0001] The present invention relates to the technical field of organic fluorine chemistry, and in particular to a fluorosulfonyl salt and a preparation method and application thereof. Background Art

[0002] Sulfonyl fluoride compounds have important applications in organic synthesis, material chemistry, chemical biology, and drug development. In particular, in 2014, Professor K. Barry Sharpless proposed the hexavalent sulfur-fluorine exchange reaction (SuFEx) as a new generation of click chemistry reaction, which provides an effective and reliable new tool for creating modular intermolecular connections. It has attracted great attention and extensive research in recent years. Fluorosulfonyl is the core group of the SuFEx click reaction. How to conveniently and efficiently obtain various sulfonyl fluoride compounds has become the basis and key to promoting the further application of the new generation of SuFEx click reactions. However, methods for introducing fluorosulfonyl groups into organic compounds are still relatively lacking. In particular, the method of introducing fluorosulfonyl groups into organic molecules by efficiently constructing C-SO2F bonds is still relatively limited, and the understanding of the bonding mode and rules of C-SO2F bonds is still insufficient, which seriously hinders people's research on sulfonyl fluoride compounds containing C-SO2F bonds.

[0003] At present, the synthesis methods of sulfonyl fluoride compounds containing C-SO2F bonds mainly include the following two methods that do not involve the construction of C-SO2F bonds: (1) oxidative fluorination or fluorine-chlorine exchange of the corresponding sulfur-containing precursor compounds. The reaction does not involve the construction of C-SO2F bonds, but the sulfur-containing precursor substrates used are often difficult to obtain or difficult to prepare. (2) Conversion from vinyl or alkynyl sulfonyl fluoride and its derivatives as building blocks. This method can generally only generate alkyl sulfonyl fluorides with two or three more carbon atoms. Therefore, the direct construction of C-SO2F bonds through fluorinated sulfonylating agents is simple, efficient, reliable and economical, and is a frontier and important research direction in the field of sulfonyl fluoride synthesis in recent years.

[0004] Through retrosynthetic analysis, we know that fluorosulfonyl can be constructed from alkyl or aryl species (C) and fluorosulfonyl synthon (FSO2) through specific reactions. - )+( + There are many reports on the method of constructing C-SO2F bond by using the bonding mode of (C·)+(·SO2F), but there is no method to construct C-SO2F bond by using nucleophilic fluorinated sulfonylating agents through (C + )+( - SO2F) to directly construct C-SO2F bonds, mainly because the fluorosulfonyl anion ·( - SO2F) is very unstable and easily decomposes into SO2 and fluoride anions. Therefore, the nucleophilic fluorinated sulfonylation reagent (M + SO2F -) are difficult to develop and their reactivity is extremely difficult to control. Based on our research interests and previous studies, we have used a large volume organic cation with high charge dispersion (R + ) and ligand-coordinated metal cations (L n M + ) has a strong stabilizing and regulating effect, effectively stabilizing the easily decomposed fluorinated sulfonyl anions (SO2F - ) to develop a series of new stable and practical nucleophilic fluorosulfonylation reagents (M + SO2F - ), and further study their reaction properties to construct a new bonding mode and method for a class of C-SO2F bonds. Summary of the invention

[0005] The purpose of the present invention is to provide a fluorosulfonyl salt and a preparation method and application thereof, so as to supplement the vacancy of nucleophilic fluorosulfonylation reagents and expand new fluorosulfonylation reactions. The invention has the advantages of cheap and readily available starting materials, mild reaction conditions, simple post-treatment and high yield, and thus has broad application prospects.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] The first aspect of the present invention provides a fluorosulfonyl salt, the chemical formula of which is R + SO2F - 、M(SO2F) Z or L x M(SO2F) Z ;

[0008] When the fluorosulfonyl salt is R + SO2F - When R + The group is any of the following:

[0009]

[0010] When the fluorosulfonyl salt is L x M(SO2F) Z When the ligand L is selected from one of the following compounds:

[0011]

[0012] wherein R, R1 and R2 are any one of hydrogen, alkyl, alkoxy, hydroxyl, carboxyl, ester, aryl, nitro, sulfonic acid, fluoroalkyl or halogen;

[0013] x=1 or 2; x=1~6;

[0014] n=1~6

[0015] The metal ion M is at least one of potassium, copper, silver, lithium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, chromium, iron, cobalt, rhodium, palladium, zinc, cadmium, mercury, aluminum, tin, lead, antimony, sodium or cesium; Z is the valence state of the metal ion M.

[0016] The second aspect of the present invention provides a method for preparing the above-mentioned fluorosulfonyl salt, comprising:

[0017] (a) Preparation of R + There are two methods for SO2F-, and the general formula is:

[0018] Method 1: RF+[SO2]→R + (SO2F) -

[0019]

[0020] Method 1: Use fluoride and sulfur dioxide source as raw materials to react in a solvent, filter after the reaction, and obtain R + SO2F- solution, vacuum remove the solvent and further wash the solid to obtain R + (SO2F)-.

[0021] Method 2: Use metal fluoride and sulfur dioxide source as raw materials to react in a solvent, filter after the reaction, and obtain M + SO2F- solution; add RX to the solution, stir at room temperature, wash with water after the reaction, extract, collect the organic phase, add anhydrous sodium sulfite to dry, and remove the solvent in vacuo to obtain R + (SO2F)-.

[0022] (b)L n M(SO2F) Z The preparation method has the general reaction formula:

[0023]

[0024] Metal fluoride and sulfur dioxide source are used as raw materials to react in a solvent, and after the reaction is completed, the mixture is filtered to obtain M + SO2F-solution;

[0025] The prepared M + The SO2F- solution is placed in a low temperature environment, and the ether solution of the ligand L is added dropwise to the solution. After the reaction is completed, the solution is allowed to stand at low temperature. Solids are precipitated, which are filtered and washed to obtain a fluorosulfonyl metal salt complex (L n M(SO2F) Z ).

[0026] Preferably, the solvent is an organic solvent, which is any one or a combination of acetonitrile, methanol, N,N-dimethylformamide, tetrahydrofuran.

[0027] More preferably, the solvent is acetonitrile.

[0028] Preferably, the sulfur dioxide source is DABSO, SO2, 2,4,6-trimethylpyridine-N-sulfinic acid, diisopropylamine-N-sulfinic acid, N-isopropyl-2-methylpropane-2-amine-N-sulfinic acid, 2,2,6,6-tetramethylpiperidine-N-sulfinic acid, N-morpholinesulfinic acid.

[0029] Further preferably, the sulfur dioxide source is: DABSO, SO2

[0030] Preferably, the reaction temperature of the fluoride and sulfur dioxide source is 25-120°C.

[0031] More preferably, the reaction temperature is 90°C.

[0032] Preferably, the reaction time is 1 to 24 hours.

[0033] More preferably, the reaction time is 12 hours.

[0034] Preferably, the molar ratio of the fluoride to the "SO2" source is 1:(1-10).

[0035] Preferably, the ligand L and the compound MF n The molar ratio is 1:(0.4~1).

[0036] Preferably, the molar ratio of the fluoride, the sulfur dioxide source, and the ligand L is 1:(1-10):1, and most preferably 1:(1-4):1.

[0037] Preferably, the molar volume ratio of the metal fluoride to the solvent is 0.05 to 0.4 mmol / mL, and most preferably 0.17 to 0.2 mol / L.

[0038] The present invention also provides an application of the fluorosulfonyl salt, wherein the fluorosulfonyl salt is used as a nucleophilic fluorosulfonylating agent for a nucleophilic fluorosulfonylating reaction.

[0039] Compared with the prior art, the present invention has the following technical advantages:

[0040] 1. The fluorosulfonyl salt prepared by the present invention has good stability and can be stored at room temperature.

[0041] 2. The method for preparing fluorosulfonyl salt proposed by the present invention is simple to operate, has mild reaction conditions, and the product is easy to obtain.

[0042] 3. The fluorosulfonyl salt of the present invention is an efficient and mild nucleophilic fluorosulfonylating agent with a wide range of substrate applicability.

[0043] 4. The method for preparing fluorosulfonyl salts is universal to most organic fluorides or inorganic fluorides, can be used for the preparation of various fluorosulfonyl salts, and has high scientific research and application value.

[0044] 5. The starting materials of the present invention, metal fluoride and sulfur dioxide, are both cheap and readily available industrial raw materials. The reaction between metal fluoride and sulfur dioxide does not produce water, so after the reaction, the reaction solvent can be removed by simple distillation to obtain anhydrous fluorosulfonyl metal salt. The reaction is simple and efficient, the post-processing is simple, the cost is low, and it is very suitable for mass preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The single crystal image of tetraphenylphosphine sulfonyl fluoride salt of Example 1 is

[0046] Figure 2 The hydrogen nuclear magnetic resonance spectrum of Example 48 is

[0047] Figure 3 The NMR fluorine spectrum of Example 48 is

[0048] Figure 4 The carbon NMR spectrum of Example 48 is DETAILED DESCRIPTION

[0049] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. The following examples are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating processes are given, but the protection scope of the present invention is not limited to the following examples. The experimental methods in the following examples that do not specify specific conditions are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, percentages and parts are calculated by weight.

[0050] Any features such as preparation methods, materials, structures or composition ratios that are not clearly described in this technical solution shall be deemed as common technical features disclosed in the prior art.

[0051] Example 1: Synthesis of sulfonyl fluoride tetraphenylphosphine salt

[0052]

[0053] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2405g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add tetraphenylphosphine chloride (0.3749g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is over, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain white solid fluorosulfonyl tetraphenylphosphine [Ph4P + (SO2F) - ]358.45mg, yield 42%.

[0054] See the single crystal image of tetraphenylphosphine sulfonyl fluoride salt for details. Figure 1 .

[0055] Comparative Example 1: Synthesis of tetraphenylphosphonium sulfonate

[0056]

[0057] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move into Temp℃ and stir th; after th, add tetraphenylphosphine chloride (0.3749g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is completed, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain the target compound. The test results of each test in this comparative example are as follows:

[0058] Table 1 Synthesis of tetraphenylphosphonium fluoride sulfonate

[0059]

[0060] Comparative Example 2: Synthesis of tetraphenylphosphonium sulfonate

[0061]

[0062] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add Solvents (10mL) as solvent. Move to 90℃ and stir for 2h; after 2h, add tetraphenylphosphine chloride (0.3749g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is completed, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain the target compound. After changing the solvent in this comparative example, the test results are as follows:

[0063]

[0064] Example 2: Synthesis of Tetra-tert-Butylammonium Fluorosulfonylate

[0065]

[0066] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add tetra-tert-butylammonium chloride (0.2773g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is over, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain white solid tetra-tert-butylammonium fluorosulfonylate [(t-Bu)4N + (SO2F) - ]195.15mg, yield 60%.

[0067] Example 3: Synthesis of tris(dimethylamino)sulfonylsulfonate

[0068]

[0069] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add tris(dimethylamino)sulfonium chloride (0.1999g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is completed, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain solid tris(dimethylamino)sulfonyl fluoride [((Me)2N)3S +( SO2F) - ]351.92 mg, yield 68%.

[0070] Example 4: Synthesis of tris(dimethylamino)fluorosulfonyl carbon

[0071]

[0072] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add tris(dimethylamino)carbon chloride (0.179g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is completed, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain solid tris(dimethylamino)sulfonylsulfonium fluoride [((Me)2N)3S +( SO2F) - ]348.24 mg, yield 70%.

[0073] Example 5: Synthesis of Tetramethylammonium Fluorosulfonylate

[0074]

[0075] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add tetramethylammonium chloride (0.1096g, 1mmol, 0.5equiv), stir at room temperature for 3h; after the reaction is over, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain solid tris(dimethylamino)sulfonylsulfonium fluoride [Me4N +( SO2F) - ]89.52mg, yield 57%.

[0076] Example 6: (2S, 5S)-1,1-dimethyl-2,5-diphenylphosphinothioic acid-1-fluorosulfonyl quaternary phosphonium salt

[0077]

[0078] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) (0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add (2S, 5S)-1,1-dimethyl-2,5-diphenylphosphino-1-iodide quaternary phosphonium salt (0.3960g, 1mmol, 0.5equiv), put in room temperature and stir for 3h; after the reaction is completed, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain 140.8mg of solid (2S, 5S)-1,1-dimethyl-2,5-diphenylphosphino-1-fluorosulfonyl quaternary phosphonium salt, with a yield of 40%.

[0079] Example 7: Synthesis of 4,4′-helical [4H-dinaphtho[2,1-c:1′,2′-e]azepane], 3,3′,5,5′-tetrahydrofluorosulfonyl

[0080]

[0081] Take a 10 mL sealed tube, put a dry magnetic bar in it, weigh silver fluoride (AgF) (0.2537 g, 2 mmol, 1 equiv), DABSO (0.4806 g, 2 mmol, 1 equiv), replace Ar three times, and add acetonitrile (10 mL) as solvent. Move to 90°C and stir for 12h; after 12h, add 4,4′-helix [4H-dinaphtho[2,1-c:1′, 2′-e]azepane], 3,3′,5,5′-tetrahydroammonium iodide (0.701g, 1mmol, 0.5equiv), and stir at room temperature for 3h; after the reaction, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain solid 4,4′-helix [4H-dinaphtho[2,1-c:1′, 2′-e]azepane], 3,3′,5,5′-tetrahydrofluorosulfonyl 414.41mg, with a yield of 63%.

[0082] Example 8: Synthesis of 3H-dinaphtho[2,1-c:1′,2′-e]phosphonium, 4,4-bis(1,1-dimethylethyl)-4,5-dihydrofluorosulfonyl

[0083]

[0084] Take a 10 mL sealed tube, put a dry magnetic bar in it, weigh silver fluoride (AgF) (0.2537 g, 2 mmol, 1 equiv), DABSO (0.4806 g, 2 mmol, 1 equiv), replace Ar three times, and add acetonitrile (10 mL) as solvent. Move to 90°C and stir for 12h; after 12h, add 3H-naphtho[2,1-c:1′,2′-e]phosphonium, 4,4-bis(1,1-dimethylethyl)-4,5-dihydrobromide (0.5065g, 1mmol, 0.5equiv), and stir at room temperature for 3h; after the reaction is completed, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain 213.62mg of solid 3H-naphtho[2,1-c:1′,2′-e]phosphonium, 4,4-bis(1,1-dimethylethyl)-4,5-dihydrofluorosulfonyl, with a yield of 42%.

[0085] Example 9: Synthesis of diphenylphosphonium [(1S)-2′-(benzyloxy) [1,1′-binaphthyl]-2-yl] (benzyl) fluorosulfonate

[0086]

[0087] Take a 10 mL sealed tube, put a dry magnetic bar in it, weigh silver fluoride (AgF) (0.2537 g, 2 mmol, 1 equiv), DABSO (0.4806 g, 2 mmol, 1 equiv), replace Ar three times, and add acetonitrile (10 mL) as solvent. Move to 90°C and stir for 12h; after 12h, add diphenylphosphonium [(1S)-2′-(benzyloxy) [1,1′-binaphthyl]-2-yl] (benzyl) chloride (0.6712g, 1mmol, 0.5equiv), and stir at room temperature for 3h; after the reaction, add water (20mL), extract with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and spin dry to obtain 603.80mg of solid diphenylphosphonium [(1S)-2′-(benzyloxy) [1,1′-binaphthyl]-2-yl] (benzyl) fluorosulfonyl, with a yield of 84%.

[0088] Example 10: Synthesis of 1,1'-((4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(N,N-bis(propargyl)-N-methylmethylamine)fluorosulfonyl

[0089]

[0090] Take a 10mL sealed tube, put in a dry magnet, weigh silver fluoride (AgF) ((0.2537g, 2mmol, 1equiv), DABSO (0.4806g, 2mmol, 1equiv), replace Ar three times, and add acetonitrile (10mL) as solvent. Move to 90℃ and stir for 12h; after 12h, add 1,1'-((4S, 5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(N,N-bis(propargyl) The mixture was stirred at room temperature for 3 h. After the reaction was completed, water (20 mL) was added and the mixture was extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered and spin-dried to obtain 255.72 mg of solid 1,1'-((4S, 5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(N,N-bis(propargyl)-N-methylmethylamine)fluorosulfonylate with a yield of 48%.

[0091] Synthesis of sulfur dioxide substitutes

[0092] Example 11: Synthesis of N-sulfinic acid-2,4,6-trimethylpyridine

[0093]

[0094] 2,4,6-trimethylpyridine (10.1 g, 83 mmol) was added to a 50 mL three-necked round-bottomed bottle. A bubbler filled with concentrated sulfuric acid was connected to the middle of the three-necked bottle through a fitting to introduce sulfur dioxide. A balloon was inserted on the far left, and the right side was directly sealed with a rubber stopper. The bottle was placed in an ethanol bath at -30°C, and SO2 was introduced (the airflow rate was about one bubble per second). The mixture was stopped after about 30 minutes. A white solid was produced. The solid was filtered, drained, and weighed to obtain 12 g of a white solid.

[0095] Example 12: Synthesis of diisopropylamine-N-sulfinic acid

[0096]

[0097] Diisopropylamine (3.61 g, 35.7 mmol) was added to a 50 mL three-necked round-bottomed bottle. A bubbler filled with concentrated sulfuric acid was connected to the middle of the three-necked bottle through a fitting to introduce sulfur dioxide. A balloon was inserted on the far left, and the right side was directly sealed with a rubber stopper. The bottle was placed in an ethanol bath at -30°C, and SO2 was introduced (the airflow rate was about one bubble per second). After about 30 minutes, a white solid was produced. The solid was filtered, drained, and weighed to obtain 3.8 g of a white solid.

[0098] Example 13: Synthesis of N-isopropyl-2-methylpropane-2-amine-N-sulfinic acid

[0099]

[0100] N-isopropyl-2-methylpropane-2-amine (1 g, 8.69 mmol) was added to a 50 mL three-necked round-bottomed bottle. A bubbler filled with concentrated sulfuric acid was connected to the middle of the three-necked bottle through a fitting to introduce sulfur dioxide. A balloon was inserted on the far left, and the right side was directly sealed with a rubber stopper. The bottle was placed in an ethanol bath at -30°C, and SO2 was introduced (the airflow rate was about one bubble per second). The mixture was stopped after about 30 minutes. A white solid was produced. The solid was filtered, drained, and weighed to obtain 0.3 g of a white solid.

[0101] Example 14: Synthesis of 2,2,6,6-tetramethylpiperidine-N-sulfinic acid

[0102]

[0103] 2,2,6,6-tetramethylpiperidine (4.1 g, 29 mmol) was added to a 50 mL three-necked round-bottomed bottle. A bubbler filled with concentrated sulfuric acid was connected to the middle of the three-necked bottle through a fitting to introduce sulfur dioxide. A balloon was inserted on the far left, and the right side was directly sealed with a rubber stopper. The bottle was placed in an ethanol bath at -30°C, and SO2 was introduced (the airflow rate was about one bubble per second). After about 30 minutes, a white solid was produced. The solid was filtered, drained, and weighed to obtain 5.8 g of a white solid.

[0104] Example 15: Synthesis of N-morpholinesulfinate

[0105]

[0106] Morpholine (4.98 g, 57 mmol) was added to a 50 mL three-necked round-bottomed bottle. A bubbler filled with concentrated sulfuric acid was connected to the middle of the three-necked bottle through a fitting to introduce sulfur dioxide. A balloon was inserted on the far left, and the right side was directly sealed with a rubber stopper. The bottle was placed in an ethanol bath at -30°C, and SO2 was introduced (the airflow rate was about one bubble per second). After about 30 minutes, a white solid was produced. The solid was filtered, drained, and weighed to obtain 6.3 g of a white solid.

[0107] Synthesis of Fluorosulfonyl Metal Salt Complexes

[0108] Example 16: Synthesis of 4,4'-di-tert-butyl-2,2'-bipyridylsulfonyl copper fluoride

[0109]

[0110] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate in -25℃, and dissolve L1 (0.1342g, 0.5mmol, 1equiv) in 8mL of ether, add it dropwise to the reaction filtrate, and put it in -25℃ and let it stand for 24h. After 24h, a blue solid precipitates at the bottom, and the solid is filtered and washed with ether. A blue solid ((tBubpy)Cu(SO2F)) is obtained with a yield of 68%.

[0111] Comparative Example 3: Synthesis of 4,4'-di-tert-butyl-2,2'-bipyridyl fluorosulfonyl copper

[0112]

[0113] Take a 10mL sealed tube and put a dry magnet in it. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide in acetonitrile solution (2mol / L) (3mL), and stir in an oil bath at 70℃ for 12h. After 12h, move the sealed tube to room temperature, and after cooling to room temperature, filter through a syringe filter. Put the filtrate in Temp℃, and dissolve 4,4'-di-tert-butyl-2,2'-bipyridine (0.1342g, 0.5mmol, 1equiv) in 8mL of ether, add it dropwise to the reaction filtrate, and put it in Temp℃ and let stand for th. After th, observe the precipitated solid, filter the solid and wash it with ether. After changing the conditions in this comparative example, the test results are as follows:

[0114] Table 2 Screening of synthesis conditions for 4,4'-di-tert-butyl-2,2'-bipyridyl fluorosulfonyl copper

[0115]

[0116] Comparative Example 4: Synthesis of 4,4'-di-tert-butyl-2,2'-bipyridyl fluorosulfonyl copper

[0117]

[0118] Take a 10mL sealed tube and put a dry magnet in it. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add a sulfur dioxide source (1mmol, 2equiv.), and stir in an oil bath at 70°C for 12h. After 12h, move the sealed tube to room temperature, and after cooling to room temperature, filter through a syringe filter. The filtrate is placed at -25°C, and 4,4'-di-tert-butyl-2,2'-bipyridine (0.1342g, 0.5mmol, 1equiv) is dissolved in 8mL of ether, added dropwise to the reaction filtrate, and placed in Temp℃ for th. After th, observe the precipitated solid, filter the solid and wash it with ether. After changing the conditions in this comparative example, the test results are as follows:

[0119] Table 3 Screening of synthesis conditions for 4,4'-di-tert-butyl-2,2'-bipyridyl fluorosulfonyl copper

[0120]

[0121] Example 17: Synthesis of 1,1'-bis(diphenylphosphino)ferrocene fluorosulfonyl copper

[0122]

[0123] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate in -25℃, dissolve 1,1'-bis(diphenylphosphino)ferrocene (0.2770g, 0.5mmol, 1equiv) in 8mL of ether, and drop it into the reaction filtrate, put it in -25℃ and let it stand for 24h. After 24h, a blue-purple solid precipitates at the bottom, and the solid is filtered and washed with ether. A blue-purple solid [dppfCu(SO2F)2] is obtained.

[0124] Example 18: Synthesis of (3R, 3A'R, 8AS, 8A'S)-2,2'-(propane-2,2-di)bis(3A, 8a-dihydro-8H-indeno[1,2-D]oxazole)sulfonyl fluoride copper

[0125]

[0126] Take a 10mL sealed tube and put a dry magnet in it. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide in acetonitrile solution (2mol / L) (3mL), and stir in an oil bath at 70°C for 12h. After 12h, move the sealed tube to room temperature, and after cooling to room temperature, filter through a syringe filter. Put the filtrate in -25°C, dissolve L3 (0.1792g, 0.5mmol, 1equiv) in 8mL of ether, add dropwise into the reaction filtrate, and then put it in -25°C and let it stand for 24h. After 24h, a purple solid precipitates at the bottom, and the solid is filtered and washed with ether. A blue-purple solid [L3Cu(SO2F)2] is obtained. Yield 63%

[0127] Example 19: Synthesis of S-(-)-1,1'-binaphthyl-2,2'-bis(diphenylphosphine)sulfonylcopper

[0128]

[0129] Take a 10mL sealed tube and put a dry magnet in it. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide in acetonitrile solution (2mol / L) (3mL), and stir in an oil bath at 70°C for 12h. After 12h, move the sealed tube to room temperature, and after cooling to room temperature, filter through a syringe filter. Put the filtrate in -25°C, dissolve L4 (0.311g, 0.5mmol, 1equiv) in 8mL of ether, add dropwise into the reaction filtrate, and then put it in -25°C and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. A solid [L4Cu(SO2F)2] is obtained, with a yield of 60%

[0130] Example 20: Synthesis of 2,2'-Bipyridyl Fluorosulfonyl Copper

[0131]

[0132] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L5 (0.0781g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L5Cu(SO2F)2] is obtained with a yield of 65%.

[0133] Example 21: Synthesis of 1,10-phenanthroline fluorosulfonyl copper

[0134]

[0135] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L6 (0.0901g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L6Cu(SO2F)2] is obtained with a yield of 69%.

[0136] Example 22: N 1 、N 1 、N 2 、N 2 -Synthesis of Tetramethylethane-1,2-diamine Fluorosulfonyl Copper

[0137]

[0138] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L7 (0.0581g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L7Cu(SO2F)2] is obtained with a yield of 69%.

[0139] Example 23: Synthesis of (9,9-dimethyl-9H-xanthen-4,5-diyl)bis(diphenylphosphine)fluorosulfonyl copper

[0140]

[0141] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L8 (0.2893g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L8Cu(SO2F)2] is obtained with a yield of 66%.

[0142] Example 24: Synthesis of 1,3-bis(diphenylphosphaneyl)propane fluorosulfonyl copper

[0143]

[0144] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L9 (0.2062g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L9Cu(SO2F)2] is obtained with a yield of 63%.

[0145] Example 25: Synthesis of 2-(diphenylphosphino)pyridinium sulfonyl copper

[0146]

[0147] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L10 (0.1316g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L9Cu(SO2F)2] is obtained with a yield of 68%.

[0148] Example 26: Synthesis of 2-(diphenylphosphino)-1-phenyl-1H-imidazole sulfonyl copper fluoride

[0149]

[0150] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L11 (0.1642g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L11Cu(SO2F)2] is obtained with a yield of 71%.

[0151] Example 27: Synthesis of (4S, 4'S)-2,2'-(cyclopropane-1,1-diyl)bis(4-tert-butyl-4,5-dihydrooxazolidine)sulfonyl fluoride copper

[0152]

[0153] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L9 (0.1461g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L9Cu(SO2F)2] is obtained with a yield of 75%.

[0154] Example 28: Synthesis of (1S, 2S)-N1, N1, N2, N2-tetramethylcyclohexane-1,2-diamine fluorosulfonyl copper

[0155]

[0156] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L13 (0.0851g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L13Cu(SO2F)2] is obtained with a yield of 75%.

[0157] Example 29: Synthesis of (S)-7,7'-bis(4,5-dihydrooxazol-2-yl)-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]fluorosulfonyl copper

[0158]

[0159] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L14 (0.1791g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L14Cu(SO2F)2] is obtained with a yield of 78%.

[0160] Example 30: Synthesis of 2,9-dimethyl-1,10-phenanthroline fluorosulfonyl copper

[0161]

[0162] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L15 (0.1041g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L15Cu(SO2F)2] is obtained with a yield of 65%.

[0163] Example 31: Synthesis of 4,7-dibromo-1,10-phenanthroline fluorosulfonyl copper

[0164]

[0165] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L16 (0.1679g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L16Cu(SO2F)2] is obtained with a yield of 62%.

[0166] Example 32: Synthesis of 1,10-phenanthroline-2,9-dicarboxylic acid fluorosulfonyl copper

[0167] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L17 (0.1340g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L17Cu(SO2F)2] is obtained with a yield of 66%.

[0168] Example 33: Synthesis of 2,9-dichloro-1,10-phenanthroline fluorosulfonyl copper

[0169]

[0170] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L18 (0.1240g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L18Cu(SO2F)2] is obtained with a yield of 61%.

[0171] Example 34: Synthesis of 1,10-phenanthroline-4,7-diol fluorosulfonyl copper

[0172]

[0173] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L19 (0.1060g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L19Cu(SO2F)2] is obtained with a yield of 69%.

[0174] Example 35: Synthesis of (S)-7,7'-di(11-phosphonyl)-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]--fluorosulfonyl copper

[0175]

[0176] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L20 (0.2200g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L20Cu(SO2F)2] is obtained with a yield of 68%.

[0177] Example 36: Synthesis of R-diphenyl[1-ferrocene(1'-dimethylaminoethyl)]phosphofluorosulfonylcopper

[0178]

[0179] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L21 (0.2207g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L21Cu(SO2F)2] is obtained with a yield of 67%.

[0180] Example 37: Synthesis of 4,4'-dimethoxy-2,2'-bipyridylsulfonyl copper fluoride

[0181]

[0182] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L22 (0.1080g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L22Cu(SO2F)2] is obtained with a yield of 69%.

[0183] Example 38: Synthesis of 6,6'-dimethyl-2,2'-bipyridylsulfonyl copper fluoride

[0184]

[0185] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L23 (0.0921g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L23Cu(SO2F)2] is obtained with a yield of 62%.

[0186] Example 39: Synthesis of [2,2'-bipyridine]-4,4'-diol fluorosulfonyl copper

[0187]

[0188] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L24 (0.0941g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L24Cu(SO2F)2] is obtained with a yield of 60%.

[0189] Example 40: Synthesis of 4,4'-dibromo-2,2'-bipyridylsulfonylcopper

[0190]

[0191] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L25 (0.1570g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L25Cu(SO2F)2] is obtained with a yield of 69%.

[0192] Example 41: Synthesis of [2,2'-bipyridine]-4,4'-dicarbonitrile fluorosulfonyl copper

[0193]

[0194] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L26 (0.1030g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L26Cu(SO2F)2] is obtained with a yield of 63%.

[0195] Example 42: Synthesis of [2,2'-bipyridine]-4,4'-dicarboxylic acid fluorosulfonyl copper

[0196]

[0197] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L29 (0.1220g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L29Cu(SO2F)2] is obtained with a yield of 69%.

[0198] Example 43: Synthesis of [2,2'-bipyridine]-4,4'-diamine fluorosulfonyl copper

[0199]

[0200] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L30 (0.0930g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L30Cu(SO2F)2] is obtained with a yield of 79%.

[0201] Example 44: Synthesis of 4,4'-dinitro-2,2'-bipyridyl fluorosulfonyl copper

[0202]

[0203] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L31 (0.1231g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L31Cu(SO2F)2] is obtained with a yield of 79%.

[0204] Example 45: Synthesis of [2,2'-bipyridine]-4,4'-diformaldehyde fluorosulfonyl copper

[0205]

[0206] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L32 (0.1061g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L32Cu(SO2F)2] is obtained with a yield of 77%.

[0207] Example 46: Synthesis of 4,4'-dimethyl-2,2'-bipyridylsulfonyl copper fluoride

[0208]

[0209] Take a 10mL sealed tube and put a dry magnet. Weigh copper difluoride (CuF2) (0.0508g, 0.5mmol, 1equiv), replace Ar three times, add sulfur dioxide acetonitrile solution (2mol / L) (3mL), put it in an oil bath at 70℃ and stir for 12h. After 12h, move the sealed tube to room temperature, cool it to room temperature, and filter it through a syringe filter. Put the filtrate at -25℃, dissolve L33 (0.0921g, 0.5mmol, 1equiv) in 8mL of ether, add it drop by drop into the reaction filtrate, and then put it at -25℃ and let it stand for 24h. After 24h, a solid precipitates at the bottom, and the solid is filtered and washed with ether. The solid [L33Cu(SO2F)2] is obtained with a yield of 80%.

[0210] Example 47: Synthesis of triphenylphosphine sulfonylsilver

[0211]

[0212] Take a 10mL sealed tube and put a dry magnet in it. Weigh silver fluoride (AgF) (0.1269g, 1mmol) and DABSO (0.2402g, 1mmol) and add them into the sealed tube in sequence. Replace Ar three times, add MeCN (5mL), and stir in an oil bath at 90℃ for 2h. After 2h, move the sealed tube to room temperature, and after cooling to room temperature, filter through a syringe filter. Put the filtrate in -25℃, dissolve L5 (0.1311g, 0.5mmol, 1equiv) in 8mL of ether, drip it into the reaction filtrate drop by drop, and then put it in -25℃ and let it stand for 24h. After 24h, a white solid precipitates at the bottom, and the solid is filtered and washed with ether. [L34AgSO2F] is obtained with a yield of 85%.

[0213] Application of Fluorosulfonyl Copper Fluorosulfonylation Reagents

[0214] 1. When X is a diazonium salt

[0215] Take the synthesis of 4-methoxybenzenesulfonyl fluoride as an example

[0216] Example 48: Synthesis of 4-methoxybenzenesulfonyl fluoride

[0217]

[0218] Take a 10 mL sealed tube, put a dry magnet in it, weigh silver fluoride (AgF) (0.1269 g, 1 mmol) and DABSO (0.1201 g, 0.5 mmol) and add them into the sealed tube in sequence. The Ar was replaced three times, and MeCN (5 mL) was added. The mixture was placed in an oil bath at 90°C and stirred for 2 h. After 2 h, the sealed tube was moved to room temperature. After cooling to room temperature, the mixture was filtered through a syringe filter. Tetrafluoroboric acid-4-methoxybenzenediazonium ester (222.06 mg, 1 mmol) and di[2-(2,4-difluorophenyl)-5-methylpyridine][2,2'-bi(tetra-tert-butylpyridine)]iridium di(hexafluorophosphate) salt (Ir[dF(Me)ppy]2(dtbbpy)PF6, 10.13 mg, 0.01 mmol) were added to the filtrate in sequence under Ar conditions. The Ar was replaced three times, and solvent MeCN (5 mL) was added. The mixture was irradiated with 440-445 nm blue light, stirred at room temperature for 12 h, the reaction was stopped, and trifluorotoluene was added as an internal standard. The F spectrum yield was 34%. 1 H NMR (500MHz, Chloroform-d) δ7.97–7.91(m,1H),7.04–6.97(m,1H),3.81(s,1H). 19 F NMR (376MHz, CDCl3): δ67.3 (s, 1F), 13 C NMR (125MHz, CDCl3) δ 164.72, 130.94, 130.88, 127.85, 127.63, 115.52, 115.51, 115.49, 115.48, 55.32, see Figure 2 , 3, 4.

[0219] Example 49: Synthesis of 4-phenylbenzenesulfonyl fluoride

[0220]

[0221] Take a 10 mL sealed tube, put a dry magnet in it, weigh silver fluoride (AgF) (0.1269 g, 1 mmol) and DABSO (0.1201 g, 0.5 mmol) and add them into the sealed tube in sequence. The Ar was replaced three times, and MeCN (5 mL) was added. The mixture was placed in an oil bath at 90°C and stirred for 2 h. After 2 h, the sealed tube was moved to room temperature. After cooling to room temperature, the mixture was filtered through a syringe filter. Tetrafluoroborate-4-phenyldiazonium ester (268 mg, 1 mmol) and di[2-(2,4-difluorophenyl)-5-methylpyridine][2,2'-bi(tetra-tert-butylpyridine)]iridium di(hexafluorophosphate) salt (Ir[dF(Me)ppy]2(dtbbpy)PF6, 10.13 mg, 0.01 mmol) were added to the filtrate in sequence under Ar conditions. The Ar was replaced three times, and solvent MeCN (5 mL) was added. The mixture was irradiated with 440-445 nm blue light, stirred at room temperature for 12 h, the reaction was stopped, and trifluorotoluene was added as an internal standard. The F spectrum yield was 36%. 1 HNMR (400MHz, CDCl3): δ7.98–7.91(m,2H),7.50–7.41(m,2H),7.32–7.26(m,1H),7.11(d,J=8.5Hz,4H); 19 FNMR (376MHz, CDCl3): δ67.1 (s, 1F); 13 CNMR (101MHz, CDCl3): δ164.3, 154.4, 131.1, 130.5, 125.9 (d, J = 24.2Hz), 125.8, 120.7, 117.8ppm.

[0222] Example 50: Synthesis of 4-nitrobenzenesulfonyl fluoride

[0223]

[0224] Take a 10 mL sealed tube, put a dry magnet in it, weigh silver fluoride (AgF) (0.1269 g, 1 mmol) and DABSO (0.1201 g, 0.5 mmol) and add them into the sealed tube in sequence. The Ar was replaced three times, and MeCN (5 mL) was added. The mixture was placed in an oil bath at 90°C and stirred for 2 h. After 2 h, the sealed tube was moved to room temperature. After cooling to room temperature, it was filtered through a syringe filter. Tetrafluoroboric acid-4-nitrodiazonium orthoester (118.46 mg, 0.5 mmol) and di[2-(2,4-difluorophenyl)-5-methylpyridine][2,2'-bi(tetra-tert-butylpyridine)]iridium di(hexafluorophosphate) salt (Ir[dF(Me)ppy]2(dtbbpy)PF6, 10.13 mg, 0.01 mmol) were added to the filtrate in sequence under Ar conditions. The Ar was replaced three times, and solvent MeCN (5 mL) was added. The mixture was irradiated with 440-445 nm blue light, stirred at room temperature for 12 h, the reaction was stopped, and trifluorotoluene was added as an internal standard. The F spectrum yield was 36%. 1 HNMR (400MHz, CDCl3): δ8.00 (d, J = 8.3 Hz, 2H), 7.71 (d, J = 8.3 Hz, 2H); 19 F NMR (376MHz, CDCl3): δ66.2 (s, 1F); 13 CNMR (101MHz, CDCl3): δ139.2, 132.7 (d, J = 25.6Hz), 129.6, 104.2ppm.

[0225] 2. When X is a halogen atom

[0226] Example 51: Synthesis of phenylmethylsulfonyl fluoride.

[0227]

[0228] 2,2'-bipyridyl fluorosulfonyl copper ((bpy)Cu(SO2F)2, 192.9 mg, 0.5 mmol), benzyl bromide (59.37 μL, 0.5 mmol) were added to the reaction flask, Ar was replaced three times, solvent MeCN (2 mL) was added, and the mixture was stirred at 60°C for 5 hours. Dichloromethane (10 mL) was added, and the mixture was washed with water three times and dried; after spin drying, the mixture was subjected to flash column chromatography to obtain white solid phenylmethylsulfonyl fluoride with a yield of 50%. 19 FNMR (376MHz,CDCl3):δ51.4ppm.

[0229] Example 52: Synthesis of (4-methoxyphenyl)methylsulfonyl fluoride

[0230]

[0231] 2,2'-bipyridyl fluorosulfonyl copper ((bpy)Cu(SO2F)2, 192.9 mg, 0.5 mmol), 4-methoxybenzyl bromide (0.1005 g, 0.5 mmol) were added to the reaction flask, Ar was replaced three times, solvent MeCN (2 mL) was added, and the mixture was stirred at 60°C for 5 hours. Dichloromethane (10 mL) was added, and the mixture was washed with water three times and dried; after spin drying, the mixture was subjected to rapid column chromatography to obtain a white solid (4-methoxyphenyl)methylsulfonyl fluoride with a yield of 69%.

[0232] Example 53: Synthesis of (3-nitrophenyl)methylsulfonyl fluoride

[0233] 2,2'-bipyridyl fluorosulfonyl copper ((bpy)Cu(SO2F)2, 192.9 mg, 0.5 mmol), 3-nitrobenzyl bromide (0.1005 g, 0.5 mmol) were added to the reaction flask, Ar was replaced three times, solvent MeCN (2 mL) was added, and the mixture was stirred at 60°C for 5 hours. Dichloromethane (10 mL) was added, and the mixture was washed with water three times and dried; after spin drying, rapid column chromatography was performed to obtain white solid (3-nitrophenyl)methylsulfonyl fluoride with a yield of 65%.

[0234] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A fluorosulfonyl salt, characterized in that: Its chemical formula is R + SO2F - 、M(SO2F) Z , L x M(SO2F) Z One of; When the fluorosulfonyl salt is R + SO2F - When R + The group is any of the following: When the fluorosulfonyl salt is L x M(SO2F) Z When the ligand L is selected from one of the following compounds: R + SO2F - and L x M(SO2F) Z In which R, R1 and R2 are each any one of hydrogen, alkyl, alkoxy, hydroxy, carboxyl, ester, aryl, nitro, sulfonic acid, fluoroalkyl or halogen; x=1 or 2, x=1 to 6, n=1 to 6; M(SO2F) Z and L x M(SO2F) Z In the invention, the metal ion M is at least one of potassium, copper, silver, lithium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, chromium, iron, cobalt, rhodium, palladium, zinc, cadmium, mercury, aluminum, tin, lead, antimony, sodium and cesium, and Z is the valence state of the metal ion M.

2. A method for preparing the fluorosulfonyl salt as claimed in claim 1, characterized in that: The following steps are involved: Preparation of R + SO2F - , including: Fluoride and sulfur dioxide source are used as raw materials to react in a solvent, and after the reaction is completed, the mixture is filtered to obtain R + SO2F - The solution, the solvent was removed in vacuo and the solid was further washed with water to obtain R + SO2F - , or, Metal fluoride and sulfur dioxide source are used as raw materials to react in a solvent, and after the reaction is completed, the mixture is filtered to obtain M + SO2F - Solution, add RX to the solution, stir at room temperature, wash with water after the reaction is completed, extract, collect the organic phase, add anhydrous sodium sulfite to dry, and remove the solvent in vacuo to obtain R + SO2F - .

3. The method for preparing the fluorosulfonyl salt according to claim 2, characterized in that: The following steps are also included: n M(SO2F) Z The preparation specifically comprises: Metal fluoride and sulfur dioxide source are used as raw materials to react in a solvent, and after the reaction is completed, the mixture is filtered to obtain M + SO2F - Solution; The prepared M + SO2F - The solution is placed in a low temperature environment, and an ether solution of ligand L is added dropwise to the solution. After the reaction is completed, the solution is allowed to stand, and solids are precipitated. The solids are filtered and washed to obtain a fluorosulfonyl metal salt complex (L n M(SO2F) Z ).

4. The method for preparing a fluorosulfonyl salt according to claim 2, characterized in that: The sulfur dioxide source is any one or more of 1,4-diazabicyclo[2.2.2]octane-1,4-diamine-1,4-disulfinic acid (DABSO), 2,4,6-trimethylpyridine-N-sulfinic acid, diisopropylamine-N-sulfinic acid, N-isopropyl-2-methylpropane-2-amine-N-sulfinic acid, 2,2,6,6-tetramethylpiperidine-N-sulfinic acid, N-morpholinesulfinic acid or sulfur dioxide gas.

5. The method for preparing a fluorosulfonyl salt according to claim 2, characterized in that: The solvent is any one or a combination of acetonitrile, tetrahydrofuran, methanol, and N,N-dimethylformamide; The washing solvent is ether or tetrahydrofuran.

6. The method for preparing a fluorosulfonyl salt according to claim 2, characterized in that: The reaction temperature of the fluoride and the sulfur dioxide source is 25 to 120° C., and the reaction time is 1 to 24 hours.

7. The method for preparing a fluorosulfonyl salt according to claim 2, characterized in that: The molar ratio of the fluoride, the sulfur dioxide source, and the ligand L is 1:(1-10):1; The molar volume ratio of the metal fluoride to the solvent is 0.05-0.4 mmol / mL.

8. The method for preparing a fluorosulfonyl salt according to claim 2, characterized in that: The X among the RX - Cl - ,Br - , I - , F - Any one or combination thereof.

9. The method for preparing a fluorosulfonyl salt according to claim 3, characterized in that: The low temperature environment is an environment with a temperature of -20 to -180°C.

10. A use of a fluorosulfonyl salt as claimed in claim 1, characterized in that: The fluorosulfonyl salt is used as a nucleophilic fluorosulfonylating agent to introduce a sulfonyl fluoride group into an organic compound.

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