Method for preparing perfluoroalkyl sulfinate ester

Abstract

The present invention discloses a method for preparing a perfluoroalkyl sulfinate ester. The method includes reacting an α-carbonyldiazo compound and a sodium perfluoroalkyl sulfinate, in an organic solvent, in the presence of anhydrous copper acetate as an optimal catalyst and tert-butyl hydroperoxide (TBHP) as a green oxidant, to obtain the perfluoroalkyl sulfinate ester. Compared to the prior art, the present method has the advantages of a wide range of reaction substrates, a short reaction time, a high reaction yield, and mild reaction conditions. The reaction does not require pre-activation of sodium perfluoroalkyl sulfinate, which can participate in the reaction directly, making reaction operations simple. The present method uses TBHP as a green oxidant and produces tert-butanol and water after reaction. Moreover, the present method avoids using a bromide or a chloride as a reaction material, and thus avoids formation of a large amount of a halide salt.

Claims

1. A method for preparing a perfluoroalkylsulfinate ester, comprising: reacting an α-carbonyldiazo compound with a sodium perfluoroalkylsulfinate in the presence of a transition metal compound as a catalyst, with a peroxide as an oxidant, in an organic solvent, to obtain the perfluoroalkylsulfinate ester, wherein the α-carbonyldiazo compound has the following chemical structural formula: ##STR00038## R.sub.1 is selected from the group consisting of naphthyl, thienyl, alkyl, alkoxy, and phenol; or R.sub.1 is ##STR00039##  R.sub.2 is selected from the group consisting of hydrogen, methyl, ethyl, tert-butyl, methoxy, phenyl, fluorine, chlorine, bromine, trifluoromethyl, hydroxyl, acetoxy, and p-toluenesulfonyloxy; wherein the sodium perfluoroalkylsulfinate is ##STR00040## wherein the transition metal compound is selected from the group consisting of a copper compound, a cobalt compound, and an iron compound; wherein the peroxide is hydrogen peroxide or tert-butyl hydroperoxide (TBHP); and wherein the perfluoroalkylsulfinate ester has the following chemical structural formula: ##STR00041##  n is 1 to 8.

2. The method according to claim 1, wherein the reaction of the α-carbonyldiazo compound with the sodium perfluoroalkylsulfinate is conducted at 50 to 90° C., for 1 to 6 hours, in the air; the transition metal compound is a copper compound; the organic solvent is petroleum ether, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, nitro methane, acetonitrile, or ethyl acetate.

3. The method according to claim 2, wherein the reaction is conducted at 60° C., in the air, for 1 hour; the copper compound is anhydrous copper acetate; and the organic solvent is ethyl acetate.

4. The method according to claim 3, further comprising after the reaction is complete, diluting with ethyl acetate, removing ethyl acetate, and conducting silica column chromatography to obtain the perfluoroalkylsulfinate ester.

5. The method according to claim 1, wherein a molar ratio of the catalyst to the α-carbonyldiazo compound is 1:10; a molar ratio of the oxidant to the α-carbonyldiazo compound is 5:1; and a molar ratio of the sodium perfluoroalkylsulfinate to the α-carbonyldiazo compound is 3:1.

Description

EXAMPLES OF THE INVENTION

(1) The following further describes the present invention with reference to the examples:

(2) The sodium trifluoromethylsulfinate, the catalyst, the oxidant, and the organic solvent of the present invention are all commercialized products and can be purchased directly. The α-carbonyldiazo compounds can be prepared with corresponding carboxylic acids, alcohols, phenols. The sodium perfluoroalkylsulfinate can be obtained from the corresponding perfluoroiodoalkane and sodium dithionite.

(3) ##STR00011##

(4) Compound 1a (0.2 mmol, 29.3 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3a, in a yield 75%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(5) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.91-7.89 (m, 2H), 7.68-7.68 (m, 1H), 7.54-7.50 (m, 2H), 5.57 (d, J=16.8 Hz, 1H), 5.38 (d, J=16.8 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.1, 134.6, 133.1, 129.1, 127.8, 67.8. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.0 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.9H.sub.7F.sub.3O.sub.3S.sup.+ Na.sup.+: 274.9960, Found: 274.9935; IR (neat, cm.sup.−1): ν 2992, 2942, 1686, 1450, 1186, 953, 753, 713, 675.

(6) ##STR00012##

(7) Compound 1b (0.2 mmol, 32.0 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3b, in a yield 61%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(8) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.79 (d, J=8.2 Hz, 2H), 7.31 (d, J=8.0 Hz, 2H), 5.54 (d, J=16.7 Hz, 1H), 5.35 (d, J=16.7 Hz, 1H), 2.44 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.7, 145.9, 130.6, 129.8, 127.9, 67.9, 21.8. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.1 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.9F.sub.3O.sub.3S+Na.sup.+: 289.0117, Found: 289.0122; IR (neat, cm.sup.−1): ν 2992, 2927, 1681, 1604, 1188, 1132, 948, 723.

(9) ##STR00013##

(10) Compound 1c (0.2 mmol, 34.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3c, in a yield 64%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(11) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.82 (d, J=8.3 Hz, 2H), 7.34 (d, J=8.3 Hz, 2H), 5.55 (d, J=16.6 Hz, 1H), 5.35 (d, J=16.6 Hz, 1H), 2.73 (q, J=7.6 Hz, 2H), 1.27 (t, J=7.6 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.7, 152.0, 130.8, 128.6, 128.1, 67.8, 29.1, 15.0. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.0 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.11F.sub.3O.sub.3S+Na.sup.+: 303.0273, Found: 303.0270; IR (neat, cm.sup.−1): ν 2972, 2935, 2880, 1681, 1190, 952, 829, 765.

(12) ##STR00014##

(13) Compound 1d (0.2 mmol, 40.5 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3d, in a yield 61%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(14) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.84 (d, J=8.5 Hz, 2H), 7.53 (d, J=8.5 Hz, 2H), 5.55 (d, J=16.7 Hz, 1H), 5.36 (d, J=16.7 Hz, 1H), 1.35 (s, 9H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.7, 158.8, 130.6, 127.8, 126.1, 67.8, 35.3, 30.9. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.0 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.13H.sub.15F.sub.3O.sub.3S+Na.sup.+: 331.0586, Found: 331.0582; IR (neat, cm.sup.−1): ν 2986, 2928, 2870, 1684, 1187, 953, 831, 718.

(15) ##STR00015##

(16) Compound 1e (0.2 mmol, 35.3 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3e, in a yield 56%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(17) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.88 (d, J=8.8 Hz, 2H), 6.98 (d, J=8.8 Hz, 2H), 5.52 (d, J=16.5 Hz, 1H), 5.33 (d, J=16.5 Hz, 1H), 3.89 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 189.5, 164.7, 130.3, 126.0, 114.3, 67.8, 55.6. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.1 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.9F.sub.3O.sub.4S+Na.sup.+: 305.0066, Found: 305.0059; IR (neat, cm.sup.−1): ν 2974, 2846, 1669, 1181, 1048, 837, 721, 636.

(18) ##STR00016##

(19) Compound 1a (0.2 mmol, 29.3 mg), 2e (0.6 mmol, 303.7 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 4d, in a yield 70%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(20) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.96-7.86 (m, 2H), 7.68-7.64 (m, 1H), 7.54-7.50 (m, 2H), (d, J=16.6 Hz, 1H), 5.34 (d, J=16.6 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.0, 134.7, 133.2, 129.1, 127.9, 67.4, not all carbons are reported due to extensive .sup.19F splitting. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −80.8 (t, J=9.9 Hz, 3F), −119.1-−121.0 (m, 2F), −121.2-−121.3 (m, 2F), −121.8-−121.9 (m, 6F), −122.72-−122.73 (m, 2F), −126.11-−126.14 (m, 2F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.16H.sub.7F.sub.17O.sub.3S+Na+: 624.9737, Found: 624.9721; IR (neat, cm.sup.−1): ν 2957, 2923, 2853, 1690, 1199, 959, 720, 687.

(21) ##STR00017##

(22) Compound 1h (0.2 mmol, 29.3 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3h, in a yield 71%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(23) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.92-7.77 (m, 2H), 7.51-7.49 (m, 2H), 5.53 (d, J=16.6 Hz, 1H), 5.32 (d, J=16.6 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.1, 141.3, 131.5, 129.5, 129.3, 67.3. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.8 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.9H.sub.6ClF.sub.3O.sub.3S+Na.sup.+: 308.9570, Found: 308.9582; IR (neat, cm.sup.−1): ν 3096, 2994, 2853, 1685, 1183, 1091, 951, 814, 703.

(24) ##STR00018##

(25) Compound 1i (0.2 mmol, 45.0 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3i, in a yield 63%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(26) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.81-7.73 (m, 2H), 7.72-7.63 (m, 2H), 5.52 (d, J=16.7 Hz, 1H), 5.31 (d, J=16.7 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.3, 132.5, 131.9, 130.1, 129.3, 67.2. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.8 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.9H.sub.6BrF.sub.3O.sub.3S+Na.sup.+: 352.9065, Found: 352.9071; IR (neat, cm.sup.−1): ν 3098, 2994, 2853, 1685, 1184, 1070, 951, 816, 708.

(27) ##STR00019##

(28) Compound 1j (0.2 mmol, 32.5 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3j, in a yield 63%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(29) .sup.1H NMR (400 MHz, DMSO) δ 10.63 (s, 1H), 7.85 (d, J=8.5 Hz, 2H), 6.90 (d, J=8.5 Hz, 2H), 5.94 (d, J=17.4 Hz, 1H), 5.80 (d, J=17.4 Hz, 1H). .sup.13C NMR (100 MHz, DMSO) δ 191.2, 163.3, 130.8, 124.4, 115.6, 71.8. .sup.19F NMR (376 MHz, DMSO) δ −79.5 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.9H.sub.7F.sub.3O.sub.4S+Na.sup.+: 290.9909, Found: 290.9901; IR (neat, cm.sup.−1): ν 3383, 2993, 2851, 1677, 1172, 1054, 962, 844, 703.

(30) ##STR00020##

(31) Compound 1k (0.2 mmol, 40.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3k, in a yield 57%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(32) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.96-7.88 (m, 2H), 7.28-7.20 (m, 2H), 5.54 (d, J=16.8 Hz, 1H), 5.35 (d, J=16.8 Hz, 1H), 2.33 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.0, 168.6, 155.4, 130.6, 129.5, 122.4, 67.8, 21.0. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.0 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.9F.sub.3O.sub.5S+Na.sup.+: 333.0015, Found: 333.0017; IR (neat, cm.sup.−1): 3109, 2991, 2939, 1751, 1682, 1136, 963, 705, 677.

(33) ##STR00021##

(34) Compound 1l (0.2 mmol, 63.3 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 31, in a yield 73%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(35) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.89-7.82 (m, 2H), 7.71 (d, J=8.2 Hz, 2H), 7.34 (d, J=8.2 Hz, 2H), 7.18-7.12 (m, 2H), 5.52 (d, J=16.8 Hz, 1H), 5.32 (d, J=16.8 Hz, 1H), 2.46 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 189.9, 153.9, 146.0, 131.8, 131.7, 130.0, 129.7, 128.4, 123.0, 67.5, 21.7. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.9 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.16H.sub.13F.sub.3O.sub.6S.sub.2+Na.sup.+: 444.9998, Found: 445.0036; IR (neat, cm.sup.−1): ν 3107, 3072, 2981, 2853, 1693, 1177, 1091, 861, 741, 667.

(36) ##STR00022##

(37) Compound 1a (0.2 mmol, 29.3 mg), 2c (0.6 mmol, 183.7 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 4b, in a yield 63%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(38) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.95-7.85 (m, 2H), 7.68-7.64 (m, 1H), 7.54-7.50 (m, 2H), 5.63 (d, J=16.7 Hz, 1H), 5.34 (d, J=16.7 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.0, 134.7, 133.2, 129.1, 127.9, 67.5, not all carbons are reported due to extensive .sup.19F splitting. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −80.8 (t, J=9.5 Hz, 3F), −119.4-−121.2 (m, 2F), −122.28-−122.32 (m, 2F), −126.1-−126.2 (m, 2F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.12H.sub.7F.sub.9O.sub.3S+Na.sup.+: 424.9864, Found: 424.9869; IR (neat, cm.sup.−1): ν 2930, 2854, 1688, 1226, 951, 758, 684, 676.

(39) ##STR00023##

(40) Compound 1m (0.2 mmol, 32.0 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3m, in a yield 66%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(41) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.71-7.67 (m, 2H), 7.48-7.46 (m, 1H), 7.42-7.38 (m, 1H), 5.55 (d, J=16.8 Hz, 1H), 5.36 (d, J=16.8 Hz, 1H), 2.43 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.3, 139.1, 135.4, 133.1, 128.9, 128.3, 125.0, 67.9, 21.2. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.0 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.9F.sub.3O.sub.3S+Na.sup.+: 289.0117, Found: 289.0114; IR (neat, cm.sup.−1): ν 2993, 2946, 2928, 1682, 1170, 970, 779, 708, 686.

(42) ##STR00024##

(43) Compound 1n (0.2 mmol, 35.3 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3n, in a yield 67%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(44) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.46-7.38 (m, 3H), 7.23-7.15 (m, 1H), 5.55 (d, J=16.8 Hz, 1H), 5.36 (d, J=16.8 Hz, 1H), 3.86 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.0, 160.1, 134.4, 130.1, 121.2, 120.2, 112.1, 67.9, 55.5. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.0 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.9F.sub.3O.sub.4S+Na.sup.+: 305.0066, Found: 305.0080; IR (neat, cm.sup.−1): ν 3026, 2995, 2840, 1681, 1469, 1172, 860, 781, 682.

(45) ##STR00025##

(46) Compound 1o (0.2 mmol, 32.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3o, in a yield 56%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(47) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.71-7.65 (m, 1H), 7.64-7.58 (m, 1H), 7.55-7.50 (m, 1H), 7.39-7.35 (m, 1H), 5.54 (d, J=16.8 Hz, 1H), 5.33 (d, J=16.8 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.0, 162.9 (d, JC-F=249.9 Hz), 135.1 (d, JC-F=6.5 Hz), 131.0 (d, JC-F=7.7 Hz), 123.6 (d, JC-F=3.2 Hz), 121.8 (d, JC-F=21.4 Hz), 114.8 (d, JC-F=22.7 Hz), 67.3. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.8 (s, 3F), −110.2 (s, 1F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.9H.sub.6F.sub.4O.sub.3S+Na.sup.+: 292.9866, Found: 292.9868; IR (neat, cm.sup.−1): ν 3092, 2921, 2851, 1689, 1176, 1126, 977, 784.

(48) ##STR00026##

(49) Compound 1p (0.2 mmol, 32.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3p, in a yield 75%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(50) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.04-8.03 (m, 1H), 7.86-7.75 (m, 2H), 7.43-7.39 (m, 1H), 5.53 (d, J=16.8 Hz, 1H), 5.33 (d, J=16.8 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.0, 137.5, 134.8, 130.9, 130.7, 126.3, 123.4, 67.3. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.8 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.9H.sub.6BrF.sub.3O.sub.3S+Na.sup.+: 352.9065, Found: 352.9087; IR (neat, cm.sup.−1): ν 3095, 2945, 2853, 1691, 1179, 1060, 971, 795.

(51) ##STR00027##

(52) Compound 1q (0.2 mmol, 42.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3q, in a yield 68%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(53) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.16 (s, 1H), 8.10 (d, J=7.9 Hz, 1H), 7.92 (d, J=7.9 Hz, 1H), 7.72-7.68 (m, 1H), 5.58 (d, J=16.8 Hz, 1H), 5.38 (d, J=16.8 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.1, 133.8, 131.9 (q, J=33.3 Hz), 131.0, 130.9, 129.9, 124.8 (q, J=3.8 Hz), 124.7, 67.3. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −63.0 (s, 3F), −78.8 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.6F.sub.6O.sub.3S+Na.sup.+: 342.9834, Found: 342.9839; IR (neat, cm.sup.−1): ν 3082, 2988, 2943, 1690, 1129, 978, 705, 690.

(54) ##STR00028##

(55) Compound 1r (0.2 mmol, 32.0 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3r, in a yield 73%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(56) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.57 (d, J=7.9 Hz, 1H), 7.50-7.46 (m, 1H), 7.36-7.28 (m, 2H), 5.45 (d, J=16.8 Hz, 1H), 5.24 (d, J=16.8 Hz, 1H), 2.56 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 193.8, 140.0, 133.1, 132.75, 132.66, 128.3, 126.0, 68.7, 21.4. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −79.1 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.9F.sub.3O.sub.3S+Na.sup.+: 289.0117, Found: 289.0115; IR (neat, cm.sup.−1): ν 2987, 2930, 1694, 1187, 945, 757, 721, 664.

(57) ##STR00029##

(58) Compound 1s (0.2 mmol, 39.3 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3s, in a yield 52%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(59) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.38 (s, 1H), 8.04-7.85 (m, 4H), 7.68-7.57 (m, 2H), 5.69 (d, J=16.6 Hz, 1H), 5.49 (d, J=16.6 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.0, 136.1, 132.2, 130.5, 129.9, 129.6, 129.4, 129.2, 127.9, 127.3, 123.0, 67.8. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.9 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.13H.sub.9F.sub.3O.sub.3S+Na.sup.+: 325.0017, Found: 325.0019; IR (neat, cm.sup.−1): ν 3065, 2990, 2942, 1681, 1193, 984, 822, 785, 740, 709.

(60) ##STR00030##

(61) Compound 1t (0.2 mmol, 30.5 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3t, in a yield 63%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(62) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.80-7.77 (m, 2H), 7.22-7.20 (m, 1H), 5.43 (d, J=16.2 Hz, 1H), 5.24 (d, J=16.2 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 184.1, 139.2, 135.6, 132.8, 128.6, 67.2. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.8 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.7H.sub.5F.sub.3O.sub.3S.sub.2+Na.sup.+: 280.9524, Found: 280.9515; IR (neat, cm.sup.−1): ν 3095, 2995, 2852, 1656, 1194, 1028, 915, 728, 710.

(63) ##STR00031##

(64) Compound 1a (0.2 mmol, 29.3 mg), 2b (0.6 mmol, 153.7 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 4a, in a yield 68%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(65) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.95-7.84 (m, 2H), 7.68-7.65 (m, 1H), 7.55-7.51 (m, 2H), 5.62 (d, J=16.7 Hz, 1H), 5.35 (d, J=16.7 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 191.0, 134.7, 133.1, 129.1, 127.9, 67.5, not all carbons are reported due to extensive .sup.19F splitting. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −80.9 (t, J=8.5 Hz, 3F), −120.0-−121.7 (m, 2F), −125.60-−125.63 (m, 2F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.7F.sub.7O.sub.3S+Na.sup.+: 374.9896, Found: 374.9912; IR (neat, cm.sup.−1): ν 2980, 2943, 1685, 1179, 1046, 947, 721, 687.

(66) ##STR00032##

(67) Compound 1v (0.2 mmol, 51.5 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3v, in a yield 63%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(68) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.87-7.81 (m, 2H), 7.77-7.70 (m, 2H), 4.91 (d, J=16.8 Hz, 1H), 4.70 (d, J=16.8 Hz, 1H), 3.73 (t, J=6.4 Hz, 2H), 2.59-2.55 (m, 2H), 2.08-2.00 (m, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 201.9, 168.5, 134.0, 131.8, 123.2, 69.4, 36.6, 35.6, 21.9. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.8 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.14H.sub.12F.sub.3NO.sub.5S+Na.sup.+: 386.0280, Found: 386.0276; IR (neat, cm.sup.−1): ν 2988, 2950, 2886, 1697, 1401, 1367, 965, 720.

(69) ##STR00033##

(70) Compound 1d′ (0.2 mmol, 56.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3d′, in a yield 71%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(71) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.79 (d, J=8.3 Hz, 2H), 7.37 (d, J=8.0 Hz, 2H), 4.79 (d, J=16.4 Hz, 1H), 4.57 (d, J=16.4 Hz, 1H), 4.42-4.39 (m, 2H), 4.28-4.25 (m, 2H), 2.46 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.3, 145.3, 132.5, 130.0, 127.9, 66.8, 63.1, 61.7, 21.6. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.7 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.12H.sub.13F.sub.3O.sub.7S.sub.2+Na.sup.+: 412.9947, Found: 412.9970; IR (neat, cm.sup.−1): ν 2958, 2924, 2852, 1759, 1173, 1127, 815, 769.

(72) ##STR00034##

(73) Compound 1x (0.2 mmol, 47.7 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3x, in a yield 52%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(74) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.95-7.87 (m, 2H), 7.76-7.67 (m, 1H), 7.62-7.59 (m, 2H), 4.91 (d, J=16.8 Hz, 1H), 4.64 (d, J=16.8 Hz, 1H), 3.47-3.43 (m, 1H), 3.01 (t, J=7.2 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 199.1, 138.5, 134.2, 129.6, 128.0, 68.4, 49.9, 31.8. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.3 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.11F.sub.3O.sub.5S.sub.2+Na.sup.+: 366.9892, Found: 366.9896; IR (neat, cm.sup.−1): ν 3066, 2998, 2849, 1737, 1188, 968, 738, 686.

(75) ##STR00035##

(76) Compound 1a′ (0.2 mmol, 40.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3a′, in a yield 70%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(77) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.91-7.89 (m, 2H), 7.68-7.57 (m, 1H), 7.53-7.49 (m, 2H), 5.54-5.43 (m, 2H), 5.05 (d, J=16.4 Hz, 1H), 4.85 (d, J=16.4 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 190.5, 166.3, 134.3, 133.6, 129.0, 127.7, 67.0, 61.9. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.7 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.9F.sub.3O.sub.5S+Na.sup.+: 333.0015, Found: 333.0020; IR (neat, cm.sup.−1): ν 3006, 2973, 2938, 1747, 1692, 1171, 755, 716, 686.

(78) ##STR00036##

(79) Compound 1b′ (0.2 mmol, 40.9 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3b′, in a yield 57%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(80) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.96-7.94 (m, 2H), 7.63-7.57 (m, 1H), 7.52-7.46 (m, 2H), 4.82 (d, J=16.2 Hz, 1H), 4.69 (t, J=6.2 Hz, 2H), 4.61 (d, J=16.2 Hz, 1H), 3.37 (t, J=6.2 Hz, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 196.2, 166.6, 136.2, 133.6, 128.7, 128.0, 62.0, 61.2, 36.9. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.7 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.14H.sub.13F.sub.3O.sub.3S+Na.sup.+: 347.0171, Found: 347.0175; IR (neat, cm.sup.−1): ν 2970, 2926, 1750, 1683, 1191, 1126, 1033, 689.

(81) ##STR00037##

(82) Compound 1c′ (0.2 mmol, 50.5 mg), 2a (0.6 mmol, 101.8 mg), Cu(OAc).sub.2 (0.02 mmol, 3.7 mg), ethyl acetate EA (2.0 mL), TBHP (1.0 mmol, 139 μL) were added to a reactor and then heated and stirred at 60° C. in the air for 1 hour. The reaction mixture was directly diluted with 2.0 mL of ethyl acetate. The solvent was removed by rotary evaporator, and silica gel column chromatography was carried out to obtain product 3c′, in a yield 67%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

(83) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.38-7.27 (m, 10H), 6.99 (s, 1H), 4.91 (d, J=16.2 Hz, 1H), 4.69 (d, J=16.2 Hz, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.7, 138.83, 138.78, 128.7, 128.4, 127.10, 127.06, 78.9, 62.2. .sup.19F NMR (376 MHz, CDCl.sub.3) δ −78.7 (s, 3F). HRMS (ESI-TOF): Anal. Calcd. For C.sub.16H.sub.13F.sub.3O.sub.4S+Na.sup.+: 381.0379, Found: 381.0376; IR (neat, cm.sup.−1): ν 3065, 3033, 2987, 1751, 1181, 1029, 743, 696.