Method for preparing cyano sulfonyl fluoride compounds

Abstract

A method for preparing cyano sulfonyl fluoride compounds is provided. Oxime ether compounds are used as free radical precursors, and under the condition of photocatalyst regulation, and in combination with the strategy of free radical sulfur dioxide insertion, the process involves photocatalytic oxidation, CC bond cleavage rings, free radical SO.sub.2 insertion and fluorination to achieve cyano/fluorosulfonyl reaction of oxime ether, yielding cyano sulfonyl fluoride products.

Claims

1. A method for preparing cyano sulfonyl fluoride compounds comprises following steps: in an organic solvent, using oxime ether compounds as free radical precursors, and in a protective atmosphere, adding photocatalyst, sulfur dioxide source and organic base free radical initiator, and stirring a mixture under an illumination condition to allow the oxime ether compounds to subject to photocatalytic oxidation and reduction to generate nitrogen free radicals, and followed by CC bond cleavage rings and free radical SO.sub.2 insertion; subsequently, adding fluorine source to undergo fluorination, and achieving cyano/fluorosulfonyl reaction of oxime ether to obtain the cyano sulfonyl fluoride compounds; wherein a general reaction formula is as follows: ##STR00028## wherein R is one of hydrogen, alkyl, aryl, ester group and heterocyclic ring, X is one of carbon, oxygen and sulfur, n is one of 1, 2 and 3, and the sulfur dioxide source is 1,4-diazabicyclo[2.2.2] octane-1,4-dium-1,4-disulfonic acid; and the fluorine source is a selective fluorine reagent, the sulfur dioxide source is DABSO, the organic base free radical initiator is tetramethylguanidine, the organic solvent is dichloroethane, the photocatalyst is 4CzIPN, Eosin Y, TPT, Mes-Acr-Me-ClO.sub.4 or Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, and photocatalytic irradiation wavelength is 460 nm.

2. The method for preparing the cyano sulfonyl fluoride compounds according to claim 1, wherein a molar ratio of the oxime ether compounds to the photocatalyst is 1:0.02-0.1, and a molar ratio of the oxime ether compounds to the sulfur dioxide source is 1:2-4.

3. The method for preparing the cyano sulfonyl fluoride compounds according to claim 1, wherein a molar ratio of the oxime ether compounds to the organic base free radical initiator is 1: 1-4.

4. The method for preparing the cyano sulfonyl fluoride compounds according to claim 1, wherein a molar ratio of the oxime ether compounds to the fluorine source is 1:1.5-4.

5. The method for preparing the cyano sulfonyl fluoride compounds according to claim 1, wherein the illumination condition is that LED lamps are used for illumination, irradiation duration is 0.8-1.2 hours, reaction temperature is room temperature, and reaction duration is 2-2.5 hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the Proton Nuclear Magnetic Resonance Spectrum (.sup.1H NMR) of the product prepared in Embodiment 4 of the present disclosure.

(2) FIG. 2 is the Carbon-13 Nuclear Magnetic Resonance Spectrum (.sup.13C NMR) of the product prepared in Embodiment 4 of the present disclosure.

(3) FIG. 3 is the Fluorine-19 Nuclear Magnetic Resonance Spectrum (.sup.19F NMR) of the product prepared in Embodiment 4 of the present disclosure.

(4) FIG. 4 is the mass spectrum of the product prepared in Embodiment 4 of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(5) In the following, the technical scheme in the embodiments of the present disclosure will be described clearly and completely with better embodiments and data. Obviously, the described embodiments are only a part of the embodiments of the present disclosure, but not the whole embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without creative labor belong to the scope of protection of the present disclosure.

(6) It should be noted that all technical terms used in the present disclosure are only for the purpose of describing specific embodiments, and are not intended to limit the scope of protection of the present disclosure. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the following embodiments of the present disclosure may be purchased from the market or prepared by existing methods.

Embodiment 1

(7) The synthetic route is:

(8) ##STR00002## 0.1 millimole (mmol) of 1a is added to a dry Schlenker reaction tube, and then 0.005 mmol of 4CzIPN, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue light-emitting diode (LED) lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(9) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 63%.

(10) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 megahertz (MHz), chloroform: 7.44-7.36 (multiplet (m), 3 hydrogen (H)), 7.29-7.27 (m, 2H), 3.93-3.86 (m, 1H), 3.81-3.75 (m, 1H), 3.72-3.65 (m, 1H), 2.97-2.86 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 137.2, 129.5, 129.0, 126.8, 116.5, 54.4 (doublet of triplets, coupling constant (d, J)=16.0 Hertz (Hz)), 37.3, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 58.8; High-Resolution Mass Spectrometry (HRMS) Electrospray Ionization (ESI) mass-to-charge ratio (m/z) calcd. for C.sub.10H.sub.11FNO.sub.2S [M+H].sup.+228.0490, found 228.0491.

Embodiment 2

(11) The synthetic route is:

(12) ##STR00003##

(13) 0.1 mmol of 1a is added to a dry Schlenker reaction tube, and then 0.005 mmol of Eosin Y, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(14) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 39%.

(15) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.44-7.36 (m, 3H), 7.29-7.27 (m, 2H), 3.93-3.86 (m, 1H), 3.81-3.75 (m, 1H), 3.72-3.65 (m, 1H), 2.97-2.86 (m, 2H); .sup.13C NMR, 101 MHZ, chloroform: 137.2, 129.5, 129.0, 126.8, 116.5, 54.4 (d, J=16.0 Hz), 37.3, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 58.8; HRMS (ESI) m/z calcd. for C.sub.10H.sub.11FNO.sub.2S [M+H].sup.+228.0490, found 228.0491.

Embodiment 3

(16) ##STR00004##

(17) 0.1 mmol of 1a is added to a dry Schlenker reaction tube, and then 0.005 mmol of TPT, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(18) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 67%.

(19) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.44-7.36 (m, 3H), 7.29-7.27 (m, 2H), 3.93-3.86 (m, 1H), 3.81-3.75 (m, 1H), 3.72-3.65 (m, 1H), 2.97-2.86 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 137.2, 129.5, 129.0, 126.8, 116.5, 54.4 (d, J=16.0 Hz), 37.3, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 58.8; HRMS (ESI) m/z calcd. for C.sub.10H.sub.11FNO.sub.2S [M+H].sup.+228.0490, found 228.0491.

Embodiment 4

(20) The synthetic route is:

(21) ##STR00005##

(22) 0.1 mmol of 1a is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-Acr-Me-ClO.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(23) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 74%.

(24) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 7.44-7.36 (m, 3H), 7.29-7.27 (m, 2H), 3.93-3.86 (m, 1H), 3.81-3.75 (m, 1H), 3.72-3.65 (m, 1H), 2.97-2.86 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 137.2, 129.5, 129.0, 126.8, 116.5, 54.4 (d, J=16.0 Hz), 37.3, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 58.8; HRMS (ESI) m/z calcd. for C.sub.10H.sub.11FNO.sub.2S [M+H].sup.+228.0490, found 228.0491.

Embodiment 5

(25) The synthetic route is:

(26) ##STR00006##

(27) 0.1 mmol of 1a is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(1-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(28) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 93%.

(29) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 7.44-7.36 (m, 3H), 7.29-7.27 (m, 2H), 3.93-3.86 (m, 1H), 3.81-3.75 (m, 1H), 3.72-3.65 (m, 1H), 2.97-2.86 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 137.2, 129.5, 129.0, 126.8, 116.5, 54.4 (d, J=16.0 Hz), 37.3, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 58.8; HRMS (ESI) m/z calcd. for C.sub.10H.sub.11FNO.sub.2S [M+H].sup.+228.0490, found 228.0491.

Embodiment 6

(30) The synthetic route is:

(31) ##STR00007##

(32) 0.1 mmol of 1b is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(33) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 69%.

(34) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.30-7.26 (m, 2H), 7.15-7.09 (m, 2H), 3.92-3.85 (m, 1H), 3.80-3.74 (m, 1H), 3.73-3.67 (m, 1H), 2.96-2.85 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 162.8 (d, J=248.9 Hz), 132.9 (d, J=3.3 Hz), 128.7 (d, J=8.3 Hz), 116.6 (d, J-21.9 Hz), 116.3, 54.4 (d, J=16.1 Hz), 36.7, 24.1; .sup.19F NMR, 377 MHz, chloroform: 59.1,-112.0; HRMS (ESI) m/zcalcd. for C.sub.10H.sub.11F.sub.2NO.sub.2S [M+H].sup.+246.0395, found 246.0393.

Embodiment 7

(35) ##STR00008##

(36) 0.1 mmol of 1c is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(37) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 95%.

(38) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.42-7.39 (m, 2H), 7.26-7.23 (m, 2H), 3.92-3.85 (m, 1H), 3.80-3.74 (m, 1H), 3.72-3.65 (m, 1H), 2.96-2.85 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 135.5, 135.0, 129.8, 128.3, 116.2, 54.2 (d, J=16.3 Hz), 36.8, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 59.2; HRMS (ESI) m/z calcd. for C.sub.10H.sub.10ClFNO.sub.2S [M+H].sup.+262.0100, found 262.0092.

Embodiment 8

(39) The synthetic route is:

(40) ##STR00009##

(41) 0.1 mmol of 1d is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(42) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 82%.

(43) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 6.31 (d, J=8.2 Hz, 2H), 5.93 (d, J=8.2 Hz, 2H), 2.66-2.59 (m, 1H), 2.542-2.48 (m, 1H), 2.45-2.38 (m, 1H), 1.72-1.59 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 136.1, 132.8, 128.5, 123.2, 116.1, 54.2 (d, J=16.5 Hz), 36.9, 23.9 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 59.2; HRMS (ESI) m/z calcd. for C.sub.10H.sub.11BrFNO2S [M+H].sup.+305.595, found 305.9592.

Embodiment 9

(44) The synthetic route is:

(45) ##STR00010##

(46) 0.1 mmol of 1e is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(47) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the light yellow oily product is obtained with a yield of 83%.

(48) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.22-7.19 (m, 2H), 6.95-6.91 (m, 2H), 3.91-3.83 (m, 1H), 3.81 (s, 3H), 3.78-3.73 (m, 1H), 3.68-3.62 (m, 1H), 2.94-2.83 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 159.8, 129.0, 128.0, 116.6, 114.8, 55.3, 54.6 (d, J=15.5 Hz), 36.6, 24.1 (d, J=1.9 Hz); .sup.19F NMR, 377 MHz, chloroform: 58.9; HRMS (ESI) m/z calcd. for C.sub.11H.sub.13FNO.sub.3S [M+H].sup.+258.0595, found 258.0596.

Embodiment 10

(49) The synthetic route is:

(50) ##STR00011##

(51) 0.1 mmol of 1f is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(52) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 80%.

(53) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 7.70 (d, J=8.1 Hz, 2H), 7.44 (d, J=8.1 Hz, 2H), 3.96-3.89 (m, 1H), 3.85-3.79 (m, 1H), 3.77-3.74 (m, 1H), 2.99-2.88 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 140.9, 131.2 (quartet, coupling constant (q, J)=32.8 Hz), 127.5, 126.5 (q, J=3.8 Hz), 123.6 (q, J=273.3 Hz), 53.9 (d, J=16.7 Hz), 37.1, 23.7 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 59.1,-62.8; HRMS (ESI) m/z calcd. for C.sub.11H.sub.10F.sub.4NO.sub.2S [M+H].sup.+296.0303, found 296.0365.

Embodiment 11

(54) The synthetic route is:

(55) ##STR00012##

(56) 0.1 mmol of 1h is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(57) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 64%.

(58) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 8.31 (d, J-8.5 Hz, 2H), 7.53 (d, J=8.5 Hz, 2H), 4.00-3.92 (m, 1H), 3.89-3.82 (m, 2H), 3.05-2.92 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 148.3, 143.8, 128.3, 124.8, 115.7, 53.9 (d, J=17.4 Hz), 37.2, 23.8 (d, J=1.6 Hz); .sup.19F NMR, 377 MHz, chloroform: 59.6; HRMS (ESI) m/z calcd. for C.sub.11H.sub.10F.sub.4NO.sub.2S [M+H].sup.+296.0303, found 296.0365.

Embodiment 12

(59) ##STR00013##

(60) 0.1 mmol of 1g is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(61) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 20:1, and the colorless oily product is obtained with a yield of 68%.

(62) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 4.12-4.05 (m, 1H), 3.86 (s, 3H), 3.83-3.76 (m, 1H), 3.43-3.37 (m, 1H), 3.04-2.94 (m, 2H); .sup.13C NMR, 101 MHZ, chloroform: 168.4, 115.7, 53.7, 50.1 (d, J=19.0 Hz), 37.1, 18.6 (d, J=1.4 Hz); .sup.19F NMR, 377 MHz, chloroform: 59.0; HRMS (ESI) m/z calcd. for C.sub.6H.sub.9FNO.sub.4S [M+H].sup.+210.0231, found 210.0227.

Embodiment 13

(63) The synthetic route is:

(64) ##STR00014##

(65) 0.1 mmol of 1i is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(66) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 76%.

(67) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.42-7.34 (m, 5H), 4.74-4.67 (m, 2H), 4.33-4.27 (m, 1H), 3.80-3.74 (m, 1H), 3.67-3.61 (m, 1H), 2.81-2.69 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 135.6, 128.9, 128.8, 128.3, 115.5, 73.2, 69.4, 54.1 (d, J=16.2 Hz), 23.0 (d, J=2.1 Hz); .sup.19F NMR, 377 MHz, chloroform: 61.5; HRMS (ESI) m/z calcd. for C.sub.11H.sub.13FNO.sub.3S [M+H].sup.+258.0595, found 258.0655.

Embodiment 14

(68) The synthetic route is:

(69) ##STR00015##

(70) 0.1 mmol of 1j is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(71) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 69%.

(72) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, dimethyl sulfoxide: 87.51 (d, J=8.7 Hz, 1H), 4.34-4.25 (m, 1H), 4.19-4.13 (m, 1H), 4.02-3.95 (m, 1H), 2.90-2.74 (m, 2H), 1.47 (s, 9H); .sup.13C NMR, 101 MHz, dimethyl sulfoxide: 8155.0, 118.0, 79.4, 53.3 (d, J=13.0 Hz), 44.0, 28.5, 23.3 (d, J=2.7 Hz); .sup.19F NMR, 377 MHz, dimethyl sulfoxide: 861.0; HRMS (ESI) m/z calcd. for C.sub.9H.sub.16FN204S [M+H].sup.+267.0810, found 267.0943.

Embodiment 15

(73) The synthetic route is:

(74) ##STR00016## 0.1 mmol of 1k is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(75) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 10:1, and the colorless oily product is obtained with a yield of 75%.

(76) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 3.60-3.55 (m, 2H), 2.66 (triplet, coupling constant (t, J)=7.0 Hz, 2H), 2.37-2.30 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 117.3, 48.9 (d, J=18.4 Hz), 19.9, 15.7; .sup.19F NMR, 377 MHz, chloroform: 55.1; HRMS (ESI) m/z calcd. for C.sub.4H.sub.7FNO.sub.2S [M+H].sup.+152.0177, found 152.0178.

Embodiment 16

(77) ##STR00017##

(78) 0.1 mmol of 11 is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(79) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 50:1, and the colorless oily product is obtained with a yield of 62%.

(80) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 4.49 (d, J=3.0 Hz, 2H), 3.72 (d, J=0.8 Hz, 2H); .sup.13C NMR, 101 MHz, chloroform: 114.3, 49.8 (d, J=21.7 Hz), 17.8; .sup.19F NMR, 377 MHz, chloroform: 52.7; HRMS (ESI) m/z calcd. for C.sub.3H.sub.4FNO.sub.2S.sub.2[M+H].sup.+168.9662, found 168.9662.

Embodiment 17

(81) The synthetic route is:

(82) ##STR00018##

(83) 0.1 mmol of 1m is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(84) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 94%.

(85) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.46-7.42 (m, 2H), 7.39-7.35 (m, 3H), 3.91-3.82 (m, 2H), 3.11 (q, J=21.7 Hz, 2H), 1.86 (s, 3H); .sup.13C NMR, 101 MHZ, chloroform: 140.0, 129.3, 128.5, 125.2, 116.5, 60.5 (d, J=13.2 Hz), 39.3, 29.4, 25.2 (d, J=1.8 Hz); .sup.19F NMR, 377 MHz, chloroform: 66.1; HRMS (ESI) m/z calcd. for C.sub.11H.sub.13FNO.sub.2S [M+H].sup.+242.0646, found 242.0643.

Embodiment 18

(86) The synthetic route is:

(87) ##STR00019##

(88) 0.1 mmol of 1n is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(89) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 10:1, and the colorless oily product is obtained with a yield of 82%.

(90) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 2.44 (t, J=6.9 Hz, 2H), 2.05-2.00 (m, 2H), 1.91-1.83 (m, 2H), 1.58 (d, J=1.0 Hz, 6H); .sup.13C NMR, 101 MHz, chloroform: 118.6, 63.7 (d, J=10.7 Hz), 36.1, 22.4, 20.2 (d, J=0.9 Hz), 17.3; .sup.19F NMR, 377 MHz, chloroform: 34.6; HRMS (ESI) m/z calcd. for C.sub.7H.sub.12FNNaO2S [M+H].sup.+216.0465, found 216.0466.

Embodiment 19

(91) The synthetic route is:

(92) ##STR00020##

(93) 0.1 mmol of 1o is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(94) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 60%.

(95) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.47-7.40 (m, 5H), 4.44 (doublet of doublets, coupling constant (dd, J)=10.8, 4.5 Hz, 1H), 2.49-2.40 (m, 1H), 2.36-2.24 (m, 3H), 1.78-1.63 (m, 2H), 1.53-1.38 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 130.2, 129.6, 129.4, 129.2, 118.9, 67.8 (d, J=12.8 Hz), 29.3, 25.6, 24.8, 16.9; .sup.19F NMR, 377 MHz, chloroform: 45.6; HRMS (ESI) m/z calcd. for C.sub.14H.sub.24FN204S [M+H].sup.+256.0803, found 256.0658.

Embodiment 20

(96) ##STR00021##

(97) 0.1 mmol of 1p is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(98) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 92%.

(99) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 4.02 (d, J=9.4 Hz, 2H), 3.92-3.88 (m, 4H), 3.04 (singlet(s), 2H), 1.45 (s, 9H); .sup.13C NMR, 101 MHz, chloroform: 155.6, 115.5, 81.0, 57.6, 55.5 (d, J=16.1 Hz), 33.1, 28.2, 25.2 (d, J=1.5 Hz); .sup.19F NMR, 377 MHz, chloroform: 64.5; HRMS (ESI) m/z calcd. for C.sub.11H.sub.18FN204S [M+H].sup.+293.0966, found 293.0920.

Embodiment 21

(100) The synthetic route is:

(101) ##STR00022##

(102) 0.1 mmol of 1q is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(103) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 3:1, and the colorless oily product is obtained with a yield of 71%.

(104) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 3.95 (s, 2H), 3.19 (t, J=12.2 Hz, 2H), 2.46 (t, J=6.7 Hz, 2H), 2.29-2.21 (m, 2H), 2.17-2.12 (m, 2H), 1.97-1.89 (m, 4H), 1.47 (s, 9H); .sup.13C NMR, 101 MHz, chloroform: 154.2, 118.5, 80.6, 65.5 (d, J-9.4 Hz), 31.3, 29.6, 28.3, 19.7 (d, J-0.93 Hz), 17.4; .sup.19F NMR, 377 MHz, chloroform: 39.3; HRMS (ESI) m/z calcd. for C.sub.14H.sub.24FN204S [M+H].sup.+335.1436, found 335.1361.

Embodiment 22

(105) The synthetic route is:

(106) ##STR00023##

(107) 0.1 mmol of Ir is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(108) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 90%.

(109) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHz, chloroform: 5.96-5.94 (m, 1H), 5.74-5.71 (m, 1H), 3.90-3.84 (m, 1H), 3.67-3.58 (m, 1H), 3.16-2.99 (m, 2H), 2.83-2.66 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 130.8, 129.1, 116.5, 62.5 (d, J=15.6 Hz), 44.8, 34.9, 22.4; .sup.19F NMR, 377 MHz, chloroform: 46.2; HRMS (ESI) m/z calcd. for CH.sub.9FNO.sub.2S [M+H].sup.+190.0333, found 190.0336.

Embodiment 23

(110) The synthetic route is:

(111) ##STR00024##

(112) 0.1 mmol of 1s is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(113) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 90%.

(114) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, chloroform: 7.36-7.28 (m, 4H), 4.14-4.05 (m, 2H), 3.64-3.51 (m, 2H), 3.08-2.94 (m, 2H); .sup.13C NMR, 101 MHz, chloroform: 138.1 (d, J=1.5 Hz), 137.8, 129.2, 128.3, 124.9, 123.4, 116.5, 63.6 (d, J=15.3 Hz), 43.2, 33.5, 21.9; .sup.19F NMR, 377 MHz, chloroform: 47.7; HRMS (ESI) m/z calcd. for ChHnFNO2S [M+H].sup.+240.0490, found 240.0490.

Embodiment 24

(115) ##STR00025##

(116) 0.1 mmol of 1t is added to a dry Schlenker reaction tube, and then 0.005 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.2 mmol of DABSO, 0.2 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(117) Then, 0.3 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 2:1, and the colorless oily product is obtained with a yield of 64%, m.p. 168-170 C.

(118) The data of hydrogen spectrum, carbon spectrum, fluorine spectrum and high resolution mass spectrum of the product are as follows: .sup.1H NMR, 400 MHZ, dichloromethane: 87.12-7.09 (m, 1H), 6.65-6.62 (m, 1H), 6.57-6.55 (m, 1H), 4.98 (s, 1H), 2.93-2.80 (m, 2H), 2.56-2.08 (m, 8H), 1.85-1.71 (m, 2H), 1.56 (s, 3H), 1.51-1.37 (m, 3H); .sup.13C NMR, 101 MHZ, dichloromethane: 8154.4, 137.9, 130.7, 126.9, 115.3, 115.2, 113.5, 70.6 (d, J=6.4 Hz), 45.2, 42.7, 42.5 (d, J=1.2 Hz), 34.2, 30.2, 27.2, 26.1, 25.6, 18.1, 14.9; .sup.19F NMR, 377 MHz, dichloromethane: 851.7, 36.9; HRMS (ESI) m/z calcd. for C.sub.18H.sub.23FNNaO3S [M+H].sup.+374.1197, found 374.1198.

Embodiment 25

(119) ##STR00026##

(120) 0.1 mmol of 1c is added to a dry Schlenker reaction tube, and then 0.002 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.3 mmol of DABSO, 0.1 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(121) Then, 0.15 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 81%.

Embodiment 26

(122) The synthetic route is:

(123) ##STR00027##

(124) 0.1 mmol of 1c is added to a dry Schlenker reaction tube, and then 0.01 mmol of Mes-(t-Bu).sub.2Acr-Ph-BF.sub.4, 0.4 mmol of DABSO, 0.4 mmol of tetramethylguanidine and 4.0 mL of dichloroethane are added under nitrogen atmosphere. A reaction mixture is irradiated with a blue LED lamp with a wavelength of 460 nm and stirred for 1 hour at room temperature.

(125) Then, 0.4 mmol of Selectfluor is added, and the reaction mixture is stirred for an addition hour. The mixture is then extracted with ethyl acetate, and the organic layers are combined. The combined organic layers are washed with saturated saline solution, dried with Na.sub.2SO.sub.4, filtered and concentrated. Further purification is performed by column chromatography or preparative thin-layer chromatography on silica gel; the eluent is petroleum ether and ethyl acetate with a volume ratio of 5:1, and the colorless oily product is obtained with a yield of 93%.

(126) The method of the present disclosure is used to synthesize a variety of functional group-substituted distal cyano sulfonyl fluoride, and its typical structure and reaction yield are shown above. The disclosed molecular structural formula of the multi-substituted cyano sulfonyl fluoride compound is not taken as a limitation on the protection scope of the present disclosure.

(127) It should be noted that when numerical ranges are involved in the present disclosure, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints may be selected. Because the steps and methods adopted are the same as those of the embodiments, the present disclosure describes optional embodiments to avoid redundancy. Although the optional embodiments of the present disclosure have been described, those skilled in the art may make additional changes and modifications to these embodiments once they know the basic inventive concepts. Therefore, the appended protection scope is intended to be interpreted as including the optional embodiments and all changes and modifications that fall within the scope of the present disclosure.

(128) Obviously, those skilled in the art may make various modifications and variations to the present disclosure without departing from the spirit and scope of the present disclosure. Thus, if these modifications and variations of the present disclosure are within the scope of protection of the present disclosure and its equivalent technology, the present disclosure is also intended to include these modifications and variations.