Supporting Information. Controllable Sulfoxidation and Sulfenylation with Organic. Thiosulfate Salts via Dual Electron- and Energy-Transfer

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1 Supporting Information Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis Yiming Li, Ming Wang, and Xuefeng Jiang*, Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai , P. R. China Index I. General Information... S2 II. Mechanistic Studies..... S3 III. General Procedures. S7 IV Procedures and Data for Table 2 and Scheme 2 S10 V. X-ray Crystallography Analysis of Compound 3u S35 VI. NMR Spectra... S36 VII. References..... S144 S1

2 I. General Information NMR Sectrum: 1 H and 13 C spectra were collected on 300 MHz 400 MHz or 500 MHz NMR spectrometers (Bruker AVANCE) using CDCl 3. Chemical shifts are reported in parts per million (ppm). Chemical shifts for protons are reported in parts per million downfield and are referenced to residual protium in the NMR solvent (CHCl 3 = δ 7.26, DMSO = δ 2.50, Acetone = δ 2.05). Chemical for carbon are reported in parts per million downfield and are referenced to the carbon resonances of solvent (CHCl 3 = δ 77.0, DMSO = δ 39.52, Acetone = δ , 29.84). Date are represented as follows: chemical shift, multiplicity (br = broad, s = singlet, d = double, t = triplet, q = quartet, m = multiplet ), coupling constants in Hertz (Hz), integration. Mass Sectroscopy: Mass spectra were in general recorded on a Shimadzu GCMS-QP2010 ΜLtra and a HP 5989A mass selective detector. Chromatography: Column chromatography was performed with silica gel ( mesh ASTM). IR: TENSOR (27) Series FT-IR Spectrometers. Solvent: MeOH, CH 3 CN, DIPEA was dried with CaH 2 and distilled using standard methods. S2

3 II. Mechanistic Studies Ultraviolet Visible Absorption Experiments Ultraviolet visible absorption experiments were performed using an Agilent Cary Eclipse UV-visible spectrophotometer. In each experiment, the varying samples were combined in MeOH/CH 3 CN = 3/1 in screw-top 1.0 cm quartz cuvettes. The concentration of each component was 1.0 x 10 5 M. Figure S1: Ultraviolet Visible Absorption Experiments. S3

4 Stern Volmer Fluorescent Quenching Experiments Fluorescence quenching studies were performed using an Agilent Cary Eclipse Fluorescence Spectrophotometer. In each experiment, the photocatalyst and varying concentrations of quencher were combined in MeOH/CH 3 CN = 3/1 in screw-top 1.0 cm quartz cuvettes. For the emission quenching of Eosin Y, the photocatalyst concentration was 1 x 10 5 M, the solution was irradiated at 520 nm, and the emission intensity was observed at 547 nm. Plots were constructed according to the Stern Volmer equation I 0 /I = 1 + kqτ 0 [Q]. Figure S2: Stern Volmer Fluorescent Quenching Experiments of Eosin Y with Different Reaction Components. S4

5 Stern Volmer Fluorescent Quenching Experiments Fluorescence quenching studies were performed using an Agilent Cary Eclipse Fluorescence Spectrophotometer. In each experiment, the photocatalyst and varying concentrations of quencher were combined in MeOH/CH 3 CN = 3/1 in screw-top 1.0 cm quartz cuvettes. For the emission quenching of Eosin Y, the photocatalyst concentration was 1 x 10 5 M, the concentrations of BQ and Co(acac) 3 are 5 x 10 5 M. The solution was irradiated at 520 nm. Figure S3: Stern Volmer Fluorescent Quenching Experiments of Eosin Y with BQ and Co(acac) 3. S5

6 Control Experiments All the reactions were conducted under standard conditions. Table S1: Control Experiments of Sulfoxidation. Table S2: Control Experiments of Sulfenylation. S6

7 III. General Procedures A. Preparation of Alkyl Thiosulfate Salts [1] A flask was charged with alkyl halides (100 mmol), sodium thiosulfate pentahydrate (120 mmol, 1.2 eq), water (50 ml) and MeOH (150 ml). The reaction mixture was stirred and heated to 65 o C. After 1 h at 65 o C, the reaction mixture was cooled to room temperature, and then concentrated on a rotovap at o C to remove MeOH and water. The resulted solid was treated with MeOH (500 ml), heated to 50 o C until most solid solved, and filtered. The filtrate was concentrated to white solid. Triturating this solid with hexanes, filtrating, and drying under vacuum. B. Preparation of Aryl Thiosulfate Salts [1] A flask was charged with aryl halides (21.2 mmol, 1.0 eq), anhydrate sodium thiosulfate (31.8 mmol, 1.5 eq) and CuI (2.12 mmol, 10 mmol%). The flask was evacuated and filled with nitrogen. DMSO (21 ml) was charged via syringe followed by DMEDA (0.46 ml, 4.24 mmol, 20 mmol%). The mixture was heated at 80 o C for 3 h. Then the reaction mixture was cooled to room temperature which followed by crystallization on addition of saturate aqueous NaCl (60 ml). The mixture was filtered and the solid was washed with saturate aqueous NaCl and hexanes. The solid was dissolved in 50 ml MeOH and stirred for 1 h at room temperaturre. The mixture was filtered and the filtrate was concentrated on a rotovap at o C. The resulted solid was dried under vacuum. The aryl thiosulfate salts could also be prepared according to Guo and Fu s method. [2] S7

8 NaHSO 3 (3 equiv.) was slowly introducted into a solution of phenyl disulfide (6.5 g, 30 mmol) in MeOH (65 ml) and H 2 O (2 ml), this mixture was refluxed overnight, then, the solvent was evaporated. Hexane (50 ml) was added and stirred for 1 hour. The mixture was filtrated and the solid was washed with hexane and Et 2 O. The trace solvent in solid was removed in vacuum. Then, the solid was extracted with boiling MeOH. After filtration and evaporation, sodium S-phenyl sulfurothioate (4.1 g, 65%) was obtained as white solid. C. General Procedures for Diaryl Iodonium Salts [3] m-chloroperbenzoic acid (75% active oxidant, 5.6 mmol) was dissolved in DCM (10 ml). To the solution was added aryl iodide (5.0 mmol) followed by slow addition of BF 3 OEt 2 (12.6 mmol) at room temperature. The resulting yellow solution was stirred at rt for 30 min and then cooled to 0 C, and arylboronic acid (5.6 mmol) was added. After 15 min of stirring at rt, the solvent was evaporated. Then, Et 2 O (20 ml) was added, the solid was filted and crystallized with DCM/ Et 2 O. If no solid was precipitated, flash column chromatography was conducted (DCM/Et 2 O = 1/1 to MeOH/DCM = 1/30). The unsymmetrical diaryl iodonium was prepared as Guant s procedure. [4] D. General Procedures for Sulfoxides To a 50 ml Schlenk tube, diaryliodium salt (0.2 mmol), thiosulfate salt (0.6 mmol), Eosin Y (2 mol%), Zn(OAc) 2 (0.4 mmol), DIPEA (0.4 mmol), MeOH/MeCN (0.3/0.1 S8

9 ml) was added, The reaction mixture was stirred and irradiated by 18 w green LED at room temperature under air (no balloon). The distant between Schlenk tube and LED is about 7 cm. After 12 h, the piston of Schlenk tube was turned and air was refilled once, if necessary, an air balloon could be added instead (for the preparation of diaryl sulfoxide, oxygen balloon was needed). After another 12 h, the reaction mixture was filtrated through celite, concentrated, purified by column chromatography on silica gel affording desired product. For detailed modification, please see the corresponding procedure. E. General Procedures for Thioethers To a 50 ml Schlenk tube, diaryliodium salt (0.2 mmol), thiosulfate salt (0.6 mmol), Eosin Y (2 mol%), Zn(OAc). 2 2H 2 O (10 mol%) was subsequently added, then the system was degassed and filled with nitrogen via Schlenk line for 5 times. Then DIPEA (0.4 mmol), MeOH (0.5 ml) was added. The reaction mixture was stirred and irradiated by 23 w CFL at room temperature for 24 h. The distant between Schlenk tube and CFL is about 7 cm. A water bath is used to maintain the reaction temperature, in which the solvent lever is same as water lever. When the reaction is completed, the mixture was filtrated through celite, concentrated, purified by column chromatography on silica gel affording desired product. S9

10 IV. Procedures and Data for Table 2 and Scheme 2 Phenyl-n-pentylsulfoxide 3a: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (123.6 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3a (32.2 mg, 82%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ 7.60 (dt, J = 8.5, 2.2 Hz, 2H), (m, 3H), 2.76 (ddd, J = 8.5, 6.6, 1.8 Hz, 2H), 1.72 (ddd, J = 8.7, 7.2, 3.0 Hz, 1H), 1.61 (dt, J = 20.2, 7.5 Hz, 1H), (m, 4H), 0.86 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.0, 130.8, 129.1, 124.0, 57.3, 30.7, 22.2, 21.8, 13.7, IR (KBr) 2957, 2930, 2860, 1637, 1618, 1466, 1458, 1443, 1384, 1089, 1041, 748, 692 cm -1. HRMS (ESI) Calcd for C 11 H 17 OS [M+H] , Found For 10 mmol scale, Diphenyliodium tetrafluoroborate (3.679 g, 10.0 mmol), sodium S-n-pentyl sulfothioate (6.180 g, 30.0 mmol), Eosin Y (138.4 mg, 0.2 mmol), Zn(OAc) 2 (5.500 g, 30.0 mmol), DIPEA (3.3 ml, 20.0 mmol), MeOH (15 ml) and MeCN (3.3 ml) was stirred at room temperature for 24 h under the irradiation of 23 w CFL. Oxygen balloon was used and bubbling. 3a (1.368 g, 76%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil. 4-(tert-butyl)-Phenyl-n-pentylsulfoxide 3b: Di-4-tert-butyl-phenyliodium tetrafluoroborate (108.5 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.3 mg, 0.6 mmol), Eosin Y (3.0 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3b (44.4 mg, 88%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), 2.88 S10

11 2.69 (m, 2H), (m, 4H), (m, 15H), 0.88 (t, J = 7.1 Hz, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ 154.5, 140.7, 126.2, 123.9, 57.3, 35.0, 31.2, 30.8, 22.3, 22.0, IR (KBr) 2961, 2930, 1560, 1385, 1261, 1150, 1100, 1050, 802 cm -1. HRMS (EI) Calcd for C 15 H 24 OS , Found (trifluoromethyl)-Phenyl-n-pentylsulfoxide 3c: Di-4-trifluoromethyl-phenyliodium trifluoromethanesulfonic salt (141.1 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.7 mg, 0.6 mmol), Eosin Y (2.6 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 3c (35.4 mg, 67%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (q, J = 8.4 Hz, 4H), (m, 2H), (m, 1H), (m, 1H), (m, 4H), (m, 3H). 19 F NMR (376 MHz, CDCl 3 ) δ C NMR (100 MHz, CDCl 3 ) δ 148.4, (q, J = 32.8 Hz), (q, J = 3.7 Hz), (m, J = Hz), 124.5, 57.1, 30.7, 22.2, 21.6, IR (KBr) 2960, 2933, 1607, 1402, 1324, 1169, 1131, 1106, 1093, 1061, 843, 700 cm -1. HRMS (EI) Calcd for C 12 H 15 F 3 OS , Found Fluoro-phenyl-n-pentylsulfoxide 3d: Di-4-fluorophenyliodium tetrafluoroborate (81.2 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.1 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3d (27.4 mg, 64%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.22 (ddd, J = 10.4, 5.9, 2.4 Hz, 2H), (m, 2H), (m, 1H), (m, 1H), 1.36 (dddd, J = 20.1, 16.7, 10.4, 4.8 Hz, 4H), 0.87 (d, J = 7.2 Hz, 3H). 13 C S11

12 NMR (100 MHz, CDCl 3 ) δ (d, J = Hz), (d, J = 3.1 Hz), (d, J = 8.8 Hz), (d, J = 22.5 Hz), 57.5, 30.7, 22.2, 21.8, F NMR (282 MHz, CDCl 3 ) δ IR (KBr) 2958, 2931, 1590, 1492, 1223, 1154, 1088, 1043, 836, 814, 521 cm -1. HRMS (EI) Calcd for C 11 H 15 FOS , Found Chloro-phenyl-n-pentylsulfoxide 3e: Di-4-chlorophenyliodium trifluoromethanesulfonic salt (100.6 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (123.6 mg, 0.6 mmol), Eosin Y (2.6 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3e (32.3 mg, 70%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.49 (d, J = 8.6 Hz, 2H), 2.76 (t, J = 7.8 Hz, 2H), (m, 1H), (m, 1H), (m, 4H), 0.87 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 142.6, 137.1, 129.5, 125.4, 57.3, 30.7, 22.2, 21.7, IR (KBr) 2958, 2930, 1475, 1390, 1261, 1083, 1043, 1011, 821, 741 cm -1. HRMS (EI) Calcd for C 11 H 15 ClOS , Found Bromo-phenyl-n-pentylsulfoxide 3f: Di-4-bromophenyliodium trifluoromethanesulfonic salt (118.5 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.1 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3f (45.7 mg, 83%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.47 (d, J = 8.5 Hz, 2H), 2.75 (t, J = 7.8 Hz, 2H), (m, 1H), (m, 1H), (m, 4H), 0.86 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz) δ (s), (s), (s), (s), (s), (s), S12

13 (s), (s), (s). IR (KBr) 2956,2930, 1469, 1385, 1065, 1043, 1008, 818, 724 cm -1. HRMS (EI) Calcd for C 11 H 15 BrOS , Found (trifluoromethyl)-Phenyl-n-pentylsulfoxide 3g: Di-3-trifluoromethyl-phenyliodium tetrafluoroborate (100.7 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (123.8 mg, 0.6 mmol), Eosin Y (3.1 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3g (46.0 mg, 87%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ 7.89 (s, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.74 (d, J = 7.7 Hz, 1H), 7.65 (t, J = 7.7 Hz, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 4H), 0.87 (t, J = 7.1 Hz, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ 145.7, (q, J = 33.2 Hz), 129.7, (q, J = 3.6 Hz), (d, J = 0.7 Hz), (m,j = Hz), (q, J = 3.8 Hz), 57.3, 30.6, 22.2, 21.7, F NMR (282 MHz, CDCl 3 ) δ IR (KBr) 2961, 2932, 1424, 1384, 1325, 1262, 1171, 1131, 1100, 1067, 1045, 803, 699 cm -1. HRMS (EI) Calcd for C 12 H 15 F 3 OS , Found Methyl-phenyl-n-pentylsulfoxide 3h: Di-2-methylphenyliodium tetrafluoroborate (79.2 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (123.6 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3h (23.9 mg, 57%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ 7.89 (dd, J = 7.7, 1.5 Hz, 1H), 7.41 (dd, J = 7.6, 0.9 Hz, 1H), 7.38 (dd, J = 7.4, 1.6 Hz, 1H), 7.19 (d, J = 7.1 Hz, 1H), (m, 2H), 2.37 (s, 3H), (m, 1H), 1.68 (s, 1H), (m, 4H), 0.88 (d, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 142.4, 134.3, 130.6, 127.2, S13

14 123.8, 55.5, 30.8, 22.3, 22.2, 18.2, IR (KBr) 2957, 2929, 2860, 1467, 1458, 1383, 1262, 1195, 1133, 1079, 1035, 800, 756, 710 cm -1. HRMS (EI) Calcd for C 12 H 18 OS , Found ,3,5-Trimethyl-phenyl-n-pentylsulfoxide 3i: Di-1,3,5-trimethylphenyliodium tetrafluoroborate (102.8 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.5 mg, 0.6 mmol), Eosin Y (2.7 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3i (23.8 mg, 50%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 3.25 (ddd, J = 12.9, 9.3, 5.3 Hz, 1H), 2.81 (ddd, J = 12.9, 9.5, 6.8 Hz, 1H), 2.53 (s, 6H), 2.28 (s, 3H), 1.78 (ddd, J = 13.5, 7.6, 4.2 Hz, 1H), 1.68 (d, J = 2.3 Hz, 1H), 1.40 (dddd, J = 24.4, 20.9, 10.4, 5.3 Hz, 4H), 0.90 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.9, 138.3, 135.1, 130.9, 52.5, 30.8, 23.4, 22.3, 21.0, 19.2, IR (KBr) 2957, 2928, 2860, 1602, 1560, 1465, 1458, 1384, 1180, 1081, 1059, 1041, 880 cm -1. HRMS (EI) Calcd for C 14 H 22 OS , Found Naphthyl-n-pentylsulfoxide 3j: Di-1-naphthyliodium tetrafluoroborate (94.1 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.1 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3j (39.9 mg, 81%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ 8.12 (dd, J = 7.3, 1.1 Hz, 1H), (m, 3H), 7.66 (dd, J = 8.1, 7.3 Hz, 1H), (m, 2H), 3.01 (ddd, J = 13.3, 9.8, 6.4 Hz, 1H), 2.81 (ddd, J = 13.3, 9.7, 5.1 Hz, 1H), (m, 1H), 1.66 (dt, J = 9.5, 5.1 Hz, 1H), (m, 4H), (m, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.8, S14

15 133.5, 131.1, 129.1, 128.9, 127.2, 126.6, 125.6, 123.1, 121.6, 56.0, 30.8, 22.3, 22.2, IR (KBr) 2956, 2929, 2859, 1505, 1465, 1401, 1382, 1189, 1066, 1045, 802, 771 cm -1. HRMS (EI) Calcd for C 15 H 18 OS , Found Thienyl-n-pentylsulfoxide 3k: Di-2-thiophenyliodium tetrafluoroborate (76.4 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (124.5 mg, 0.6 mmol), Eosin Y (3.0 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3k (20.6 mg, 50%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ 7.65 (dd, J = 5.0, 1.2 Hz, 1H), 7.46 (dd, J = 3.7, 1.3 Hz, 1H), 7.12 (dd, J = 5.0, 3.7 Hz, 1H), 3.11 (ddd, J = 12.8, 8.6, 6.3 Hz, 1H), 2.93 (ddd, J = 12.8, 8.7, 7.0 Hz, 1H), (m, 2H), (m, 4H), 0.89 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.0, 130.9, 129.7, 127.3, 58.3, 30.7, 22.4, 22.2, IR (KBr) 1647, 1383, 1189, 1151, 1130, 1112, 1037, 1017, 825 cm -1. HRMS (EI) Calcd for C 9 H 14 OS , Found Phenylbenzylsulfoxide 3l: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-benzyl sulfothioate (135.7 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3l (24.6 mg, 57%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), (m, 3H), 6.91 (dd, J = 7.9, 1.4 Hz, 2H), 4.02 (d, J = 12.6 Hz, 1H), 3.92 (d, J = 12.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 142.7, 131.1, 130.3, 129.1, 128.8, 128.4, 128.2, 124.4, IR (KBr) 3059, 2960, 2910, 1494, 1454, 1442, 1414, 1390, 1086, 1037, 1021, 998, 766, 744, 692, 494, 480 cm -1. HRMS (EI) Calcd for C 13 H 12 OS , Found S15

16 Phenyl-2-ethoxyethylsulfoxide 3m: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-n-etheryl sulfothioate (124.9 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3m (25.0 mg, 63%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 3.89 (dt, J = 10.6, 6.6 Hz, 1H), (m, 1H), 3.52 (p, J = 7.1 Hz, 2H), (m, 2H), 1.20 (t, J = 7.0 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 144.1, 131.0, 129.2, 123.9, 66.8, 63.1, 58.3, IR (KBr) 2974, 2927, 2869, 1477, 1444, 1376, 1121, 1108, 1088, 1046, 748, 693 cm -1. HRMS (EI) Calcd for C 10 H 14 O 2 S , Found Phenyl-(tetrahydrofuran-2-yl)methylsulfoxide 3n: Diphenyliodium tetrafluoroborate (73.3 mg, 0.2 mmol), sodium S- (tetrahydrofuran-2-yl)methyl sulfothioate (133.0 mg, 0.6 mmol), Eosin Y (2.7 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 2-((phenylsulfinyl)methyl)tetrahydrofuran 3n (25.2 mg, 60%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 2H), (m, 1H), 3.07 (ddd, J = 16.6, 13.0, 5.1 Hz, 1H), 2.85 (ddd, J = 22.3, 13.0, 7.4 Hz, 1H), (m, 1H), (m, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , 73.76, 72.88, 66.26, 66.20, 64.37, 62.80, 31.47, 31.23, 25.64, The 1 H NMR and 13 C NMR indicated the existence of diastereoisomers which caused by sulfoxide group. IR (KBr) 2961, 1444, 1385, 1324, 1167, 1087, 1043, 803, 751, 693 cm -1. HRMS (EI) S16

17 Calcd for C 11 H 14 O 2 S , Found Phenyl-4-butanenitrilesulfoxide 3o: Di-phenyliodium tetrafluoroborate (85.6 mg, 0.2 mmol), sodium S- butanenitrile sulfothioate (130.3 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3o (23.9 mg, 62%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.4 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ = 7.61 (dd, J=7.8, 1.7, 2H), (m, 3H), 2.99 (ddd, J=13.5, 8.7, 6.7, 1H), (m, 1H), (m, 2H), (m, 1H), 1.99 (dd, J=14.4, 7.6, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ = 142.9, 131.3, 129.4, 123.8, 118.3, 54.5, 18.4, IR (film) 3449, 3059, 2930, 2248, 1725, 1642, 1445, 1729, 1084, 1040, 750, 693 cm -1. HRMS (EI) Calcd for C 10 H 11 NOS , Found Phenyl-4-(methylbutanoate)sulfoxide 3p: Diphenyliodium tetrafluoroborate (73.9 mg, 0.2 mmol), sodium S-methyl butanoatyl sulfothioate (141.5 mg, 0.6 mmol), Eosin Y (2.7 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3p (33.4 mg, 74%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.4 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 3.63 (s, 3H), (m, 2H), 2.43 (td, J = 7.1, 1.6 Hz, 2H), (m, 1H), (m, 1H). 13 C NMR (125 MHz, CDCl 3 ) δ 172.7, 143.2, 131.0, 129.2, 123.9, 55.8, 51.6, 32.4, IR (KBr) 2952, 1735, 1477, 1443, 1372, 1318, 1264, 1213, 1176, 1071, 1045, 750, 693 cm -1. HRMS (EI) Calcd for C 11 H 14 O 3 S , Found S17

18 Phenyl-6-(hexan-1-ol)sulfoxide 3q : Diphenyliodium tetrafluoroborate (73.8 mg, 0.2 mmol), sodium S-1-hydroxyl-6-butyl sulfothioate (143.2 mg, 0.6 mmol), Eosin Y (2.9 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 18 w green LED. 3q (34.9 mg, 77%) was obtained through column chromatography (DCM/MeOH = 50/1) as a colorless oil, R f = 0.5 (DCM/MeOH = 30/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 3.60 (dd, J = 11.1, 4.6 Hz, 2H), 2.77 (tt, J = 7.6, 3.7 Hz, 2H), 1.97 (s, 1H), 1.69 (ddt, J = 17.4, 11.0, 5.3 Hz, 2H), 1.53 (dd, J = 13.9, 6.9 Hz, 2H), (m, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 143.7, 130.9, 129.2, 124.0, 62.4, 57.1, 32.3, 28.3, 25.3, IR (KBr) 2933, 2859, 1444, 1385, 1185, 1126, 1087, 1072, 1034, 750, 692 cm -1. HRMS (EI) Calcd for C 12 H 18 O 2 S , Found Phenyl-4-methyl-phenylsulfoxide 3r: Diphenyliodium tetrafluoroborate (74.1 mg, 0.2 mmol), sodium S- 4-methylphenyl sulfothioate (135.7 mg, 0.6 mmol), Eosin Y (3.3 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature in air for 12 h then in oxygen (1 atm) for 24 h under the irradiation of 18 w green LED. 3r (23.9 mg, 68%) was obtained through column chromatography (PE/EA = 2/1) as a white solid, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 3H), (m, 2H), 2.28 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.8, 142.4, 141.6, 130.8, 130.0, 129.2, 124.9, 124.6, IR (KBr) 3051, 2919, 1593, 1578, 1561, 1385, 1307, 1182, 1088, 1050, 1015, 814, 749, 705, 687, 529 cm -1. HRMS (EI) Calcd for C 13 H 12 OS , Found S18

19 Phenyl-4-chloro-phenylsulfoxide 3s: Diphenyliodium tetrafluoroborate (74.4 mg, 0.2 mmol), sodium S- 4-chlorophenyl sulfothioate (148.9 mg, 0.6 mmol), Eosin Y (2.7 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature in air for 12 h then in oxygen (1 atm) for 24 h under the irradiation of 18 w green LED. 1-chloro-4-(phenylsulfinyl)benzene 3s (30.8 mg, 65%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 3H), (m, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ 145.2, 144.1, 137.3, 131.4, 129.6, 129.5, 126.1, IR (KBr) 2950, 2923, 1572, 1474, 1443, 1386, 1261, 1086, 1047, 1022, 1010, 820, 751, 739, 703, 689, 554, 517 cm -1. HRMS (EI) Calcd for C 12 H 9 ClOS , Found Chloro-phenyl-3-methoxy-phenylsulfoxide 3t : Di-4-chlorophenyliodium tetrafluoroborate (100.1 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (148.8 mg, 0.6 mmol), Eosin Y (2.7 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature in air for 12 h then in oxygen (1 atm) for 24 h under the irradiation of 18 w green LED. 3t (37.4 mg, 70%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.4 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 7.35 (t, J = 7.9 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 3.82 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.5, 146.6, 144.2, 137.3, 130.4, 129.6, 126.1, 117.6, 116.8, 109.1, IR (KBr) 3059, 2962, 1594, 1577, 1475, 1430, 1388, 1284, 1249, 1236, 1183, 1092, 1045, 1011, 822, 783, 740, 685, 594, 510 cm -1. HRMS (EI) Calcd for C 13 H 11 ClO 2 S , Found S19

20 4-Bromo-phenyl-3-methoxy-phenylsulfoxide 3u : Di-4-bromophenyliodium tetrafluoroborate (104.7 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (145.3 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature in air for 12 h then in oxygen (1 atm) for 24 h under the irradiation of 18 w green LED. 3u (44.8 mg, 72%) was obtained through column chromatography (PE/EA = 2/1) as a white solid, R f = 0.4 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ = (m, 2H), (m, 2H), 7.35 (t, J=8.0, 1H), (m, 1H), 7.15 (d, J=7.7, 1H), (m, 1H), 3.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ = 160.4, 146.4, 144.8, 132.5, 130.4, 126.2, 125.5, 117.6, 116.8, 109.0, 55.5 (d, J=2.3). IR (film) 3057, 3006, 2938, 2836, 1593, 1575, 1475, 1427, 1384, 1316, 1283, 1243, 1179, 1088, 1040, 1006, 816, 781, 721, 681 cm -1. HRMS (EI) Calcd for C 13 H 11 O 2 SBr , Found Fluoro-phenyl-phenylsulfoxide 3v : Di-4-fluorophenyliodium tetrafluoroborate (80.7 mg, 0.2 mmol), sodium phenyl sulfothioate (127.3 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature in air for 12 h then in oxygen (1 atm) for 48 h under the irradiation of 18 w green LED. 3v (27.3 mg, 62%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.5 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ = 7.63 (ddd, J=9.6, 4.9, 1.8, 4H), (m, 3H), 7.14 (t, J=8.6, 2H). 19 F NMR (376 MHz, CDCl 3 ) δ = C NMR (100 MHz, CDCl 3 ) δ = (d, J=251.9), 145.3, (d, J=3.1), 131.2, 129.4, (d, J=9.0), 124.6, (d, J=22.6). IR (film) 3060, 2957, 2927, 2855, 1589, 1491, 1444, 1226, 1153, 1089, 1045, 833, 748, 705, 689 cm -1. HRMS (EI) Calcd for C 12 H 9 OSF , Found S20

21 4-Ethoxycarbonyl-phenyl-phenylsulfoxide 3w: Bis(4-(ethoxycarbonyl)phenyl)iodonium tetrafluoroborate (102.4 mg, 0.2 mmol), sodium phenyl sulfothioate (127.3 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (73.4 mg, 0.4 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature in air for 12 h then in oxygen (1 atm) for 48 h under the irradiation of 18 w green LED. 1-((4-bromophenyl)sulfinyl)-3-methoxybenzene 3w (30.2 mg, 55%) was obtained through column chromatography (PE/EA = 2/1) as a colorless oil, R f = 0.2 (PE/EA = 2/1); 1 H NMR (400 MHz, CDCl 3 ) δ = 8.11 (d, J=8.3, 2H), 7.71 (d, J=8.2, 2H), (m, 2H), (m, 3H), 4.36 (q, J=7.1, 2H), 1.37 (t, J=7.1, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ = 165.5, 150.3, 145.0, 132.7, 131.5, 130.4, 129.5, 124.8, 124.3, 61.4, IR (film) 2980, 2928, 1719, 1595, 1444, 1397, 1368, 1275, 1173, 1088, 1049, 1015, 855, 799, 765, 749, 697 cm -1. HRMS (EI) Calcd for C 15 H 14 O 3 S , Found (3aR,5R,6S,6aR)-5-((R)-2,2-Dimethyl-1,3-diox olan-4-yl)-2,2-dimethyltetrahydrofuro[2,3-d][ 1,3]dioxol-6-yl 4-(phenylsulfinyl)butanoate 3x: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S- (3aR,5R,6S,6aR)-5-((R)-2,2-dimethyl-1,3-dioxol an-4-yl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-yl butyrate sulfothioate (278.7 mg, 0.6 mmol), Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc) 2 (110.1 mg, 0.6 mmol), DIPEA (66 μl, 0.4 mmol), MeCN (0.4 ml) was stirred at room temperature for 24 h under the irradiation of 23 w CFL. 3x (68.8 mg, 84%) was obtained through column chromatography (DCM/MeOH = 50/1) as a colorless oil, R f = 0.5 (DCM/MeOH = 30/1); 1 H NMR (300 MHz, CD 3 CN) δ (m, 5H), (m, 1H), 5.09 (d, J = 2.5 Hz, 1H), 4.49 (t, J = 3.7 Hz, 1H), (m, 2H), 4.02 (dd, J = 8.4, 5.8 Hz, 1H), (m, 1H), 2.93 (ddt, J = 12.2, 9.5, 6.1 Hz, S21

22 1H), (m, 1H), (m, 2H), 1.98 (s, 1H), 1.81 (qdd, J = 14.1, 7.2, 2.5 Hz, 1H), 1.46 (s, 3H), 1.34 (d, J = 1.0 Hz, 3H), 1.27 (s, 3H), 1.24 (d, J = 4.1 Hz, 3H). 13 C NMR (125 MHz, CD 3 CN) δ (d, J = 1.2 Hz), (d, J = 2.8 Hz), 129.3, 124.0, 111.8, 108.7, (d, J = 0.8 Hz), 83.1, 79.5, 76.1, 72.5, 66.4, 32.3 (d, J = 0.7 Hz), 25.9, 25.9, 25.4, 24.5, 17.3, IR (KBr) 2987, 2936, 1743, 1457, 1383, 1374, 1216, 1132, 1075, 1045, 1023, 845, 750 cm -1. HRMS (ESI) Calcd for C 22 H 31 O 8 S, [M+H] , Found (2S,3R,4S,5S,6R)-6-((benzoyloxy)methyl)-2-Methoxy-5-( (4-(phenylsulfinyl)butanoyl)oxy)tetrahydro-2H-pyran-3, 4-diyl dibenzoate 3y: Diphenyliodium tetrafluoroborate (64.0 mg, 0.17 mmol), sodium S- (2S,3R,4S,5S,6R)-6-((benzoyloxy)methyl)-5-(butyryloxy)- 2-methoxytetrahydro-2H-pyran-3,4-diyl dibenzoate sulfothioate (351.8 mg, 0.51 mmol), Eosin Y (5.1 mg, 10.2*10-3 mmol), Zn(OAc) 2 (92.5 mg, 0.51 mmol), DIPEA (55.5 μl, 0.34 mmol), MeCN (0.4 ml) was stirred at room temperature for 24 h under the irradiation of 23 w CFL. 3y (72.7 mg, 61%) was obtained through column chromatography (DCM/MeOH = 50/1) as a colorless oil, R f = 0.5 (DCM/MeOH = 30/1); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 2H), (m, 15H), 5.83 (dt, J = 10.7, 3.3 Hz, 1H), 5.78 (d, J = 3.4 Hz, 1H), 5.21 (dd, J = 3.4, 2.3 Hz, 1H), (m, 2H), 4.35 (ddd, J = 11.9, 10.1, 5.4 Hz, 1H), 3.46 (t, J = 3.2 Hz, 3H), (m, 4H), (m, 1H), 1.88 (ddd, J = 9.3, 8.2, 4.5 Hz, 1H). 13 C NMR (125 MHz, CD 3 CN) δ , , , , , , , 129,84, , 129,66, , , , , , 97.61, 68.89, 68.82, 68.67, 68.41, 68.32, 66.40, 62.08, 55.72, 55.60, 55.34, 32.43, 32.39, 17.52, The 13 C NMR indicated the existence of diastereoisomers which caused by sulfoxide group. IR (KBr) 2962, 1724, 1602, 1451, 1316, 1269, 1177, 1110, 1097, 1070, 1047, 1028, 804, 712 cm -1. HRMS (ESI) Calcd for C 38 H 37 O 11 S, [M+H] , Found S22

23 2-Methyl-5-nitro-1-(2-(phenylsulfinyl)ethyl)-1H-imida zole 3z: Diphenyliodium tetrafluoroborate (73.8 mg, 0.2 mmol), sodium S- 2-methyl-5-nitro-1-propyl-1H-imidazole sulfothioate (173.6 mg, 0.6 mmol), Eosin Y (2.6 mg, 4*10-3 mmol), Zn(OAc) 2 (110.9 mg, 0.6 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.3 ml) and MeCN (0.1 ml) was stirred at room temperature for 24 h under the irradiation of 23 w CFL. 3z (27.9 mg, 50%) was obtained through column chromatography (DCM/MeOH = 50/1) as a white solid, R f = 0.4 (DCM/MeOH = 30/1); 1 H NMR (500 MHz, CDCl 3 ) δ 6.76 (dd, J = 10.7, 7.2 Hz, 4H), 6.70 (s, 1H), 3.91 (t, J = 6.9 Hz, 2H), 2.76 (t, J = 6.9 Hz, 2H), 1.82 (s, 3H). 13 C NMR (125 MHz, CD 3 CN) δ 150.5, 138.3, 133.6, 132.9, 129.9, 129.3, 127.2, 46.1, 133.6, IR (KBr) 2953, 2902, 2350, 2332, 1529, 1466, 1426, 1384, 1364, 1262, 1188, 1146, 1086, 1045, 830, 770, 701 cm -1. HRMS (EI) Calcd for C 12 H 13 N 3 O 3 S , Found Phenyl(pentyl)sulfane 4a: Diphenyliodium tetrafluoroborate (73.5 mg, 0.2 mmol), sodium S- n-pentyl sulfothioate (123.6 mg, 0.6 mmol) Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.3 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred under nitrogen at room temperature for 24 h under the irradiation of 23 W CFL. 4a [5] (30.3 mg, 84%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ = (m, 2H), 7.19 (t, J=7.8, 2H), 7.08 (d, J=7.1, 1H), (m, 2H), (m, 2H), (m, 4H), 0.82 (t, J=7.2, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ = 137.1, 128.8, 128.8, 125.6, 33.5, 31.0, 28.8, 22.2, IR (film) 2957, 2932, 2866, 1468, 1446, 1306, 1152, 1088, 1039, 749, 694, cm -1. S23

24 (4-bromophenyl)(pentyl)Sulfane 4b: Di(4-bromo)phenyliodium tetrafluoroborate (119.0 mg, 0.2 mmol), sodium S-n-pentyl sulfothioate (123.6 mg, 0.6 mmol) Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4b (45.2 mg, 87%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.23 (dd, J = 12.7, 6.0 Hz, 2H), (m, 2H), (m, 2H), (m, 4H), 0.91 (t, J = 7.0 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.0, 133.4, 122.2, 92.0, 39.2, 30.7, 28.9, 22.3, IR (KBr) 2980, 2910, 1560, 1420, 1385, 1261, 1102, 1043, 801 cm -1. HRMS (EI) Calcd for C 11 H 15 BrS , Found Methyl(phenyl)sulfane 4c: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-n-methyl sulfothioate (150.0 mg, 1.0 mmol) Eosin Y (2.5 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4c (22.3 mg, 90%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), 2.53 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 138.3, 128.7, 126.4, 124.9, IR (film) 2963, 1259, 1084, 1013, 792, 693 cm -1. Phenyl-6-(hexan-1-ol)sulfane 4d : Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-1-hydroxyl-6-butyl sulfothioate (143.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4d (21.0 mg, 50%) was obtained through column chromatography (PE/EA = 5/1) as a S24

25 colorless oil, R f = 0.5 (PE/EA = 5/1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), 7.09 (dt, J = 9.1, 4.3 Hz, 1H), 3.55 (t, J = 6.6 Hz, 2H), (m, 2H), 1.58 (dd, J = 14.9, 7.6 Hz, 2H), 1.48 (dd, J = 14.3, 6.8 Hz, 2H), (m, 2H), (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 136.9, 128.9, 128.8, 125.7, 62.8, 33.5, 32.6, 29.1, 28.5, IR (KBr) 2931, 1589, 1576, 1559, 1474, 1466, 1458, 1420, 1247, 1091, 1043, 800, 754, 598 cm -1. HRMS (EI) Calcd for C 12 H 18 OS , Found Phenyl-2-acetonitrile-sulfane 4e: Diphenyliodium tetrafluoroborate (74.3 mg, 0.2 mmol), sodium S-acetonitrile sulfothioate (114.8 mg, 0.6 mmol) Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4e [6] (17.9 mg, 60%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 3.57 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 132.4, 132.1, 129.6, 129.0, 116.4, IR (KBr) 2964, 2929, 2361, 1578, 1478, 1458, 1440, 1400, 1261, 1088, 1039, 1025, 803, 745, 691 cm -1. Benzyl(phenyl)sulfane 4f: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-benzyl sulfothioate (135.8 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. benzyl(phenyl)sulfane 4f [7] (29.2 mg, 73%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 9H), 7.21 (dt, J = 9.4, 4.3 Hz, 1H), 4.15 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 137.4, 136.3, 129.7, 128.8, 128.8, 128.5, 127.2, 126.3, IR (KBr) 2970, 2900, 1589, 1576, 1495, 1479, 1454, 1438, 1420, 1383, 1247, 1231, 1072, 1042, 1026, 799, 772, 739, 690 cm -1. S25

26 (4-(tert-butyl)benzyl)(phenyl)Sulfane 4g: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-4-(tert-butyl)benzyl sulfothioate (169.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4g [8] (30.9 mg, 60%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.26 (d, J = 1.8 Hz, 1H), 7.24 (d, J = 1.7 Hz, 2H), (m, 5H), 7.12 (dd, J = 6.8, 1.8 Hz, 1H), 4.05 (s, 2H), 1.23 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 150.1, 136.8, 134.2, 129.2, 128.8, 128.5, 126.1, 125.5, 38.4, 34.5, IR (KBr) 2962, 2925, 2867, 1480, 1458, 1437, 1411, 1262, 1092, 1025, 1018, 843, 803, 735, 690, 561 cm -1. Phenyl(3-phenylprop-2-yn-1-yl)sulfane 4h: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-(prop-1-yn-1-ol)phenyl sulfothioate (150.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4h [9] (20.6 mg, 46%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.44 (d, J = 7.3 Hz, 2H), (m, 4H), 7.20 (dd, J = 5.1, 1.9 Hz, 4H), 3.77 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 135.2, 131.7, 130.6, 128.9, 128.2, 128.2, 127.0, 122.9, 85.2, 83.7, IR (KBr) 2950, 2910, 1597, 1582, 1489, 1479, 1439, 1265, 1225, 1087, 1070, 1054, 1025, 756, 740, 690 cm -1. (3-methoxyphenyl)(phenyl)Sulfane 4i: Diphenyliodium tetrafluoroborate (74.3 mg, 0.2 mmol), sodium S- 3-methyloxyl sulfothioate (134.4 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), S26

27 MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. (3-methoxyphenyl)(phenyl)sulfane 4i [ 10 ] (33.3 mg, 77%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.30 (dd, J = 5.3, 3.3 Hz, 2H), (m, 2H), (m, 2H), 6.83 (d, J = 7.7 Hz, 1H), (m, 1H), (m, 1H), 3.67 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.1, 137.2, 135.3, 131.4, 129.9, 129.2, 127.2, 123.0, 115.9, 112.8, IR (KBr) 2970, 2943, 1590, 1576, 1476, 1439, 1425, 1283, 1072, 1043, 860, 775, 689 cm -1. For 10 mmol scale, Diphenyliodium tetrafluoroborate (3.680 mg, 10.0 mmol), sodium S-3-methyloxyl sulfothioate (7.260 g, 30.0 mmol), Eosin Y (125 mg, 0.2 mmol), Zn(OAc). 2 2H 2 O (219.0 mg, 1.0 mmol), DIPEA (3.3 ml, 20 mmol), MeOH (15 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. (3-methoxyphenyl)(phenyl)sulfane 4i (1.361 g, 63%) was obtained through column chromatography (PE) as a colorless oil. (4-fluorophenyl)(3-methoxyphenyl)Sulfane 4j: Di-(4-fluoro)phenyliodium tetrafluoroborate (80.8 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4j [11] (30.4 mg, 65%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.41 (dd, J = 8.6, 5.3 Hz, 2H), 7.19 (t, J = 8.0 Hz, 1H), 7.04 (t, J = 8.6 Hz, 2H), 6.83 (d, J = 7.8 Hz, 1H), (m, 2H), 3.76 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ (d, J = Hz), 160.0, 138.1, (d, J = 8.2 Hz), 129.9, (d, J = 3.4 Hz), 121.8, (d, J = 22.0 Hz), 114.9, 112.3, F NMR (282 MHz, CDCl 3 ) δ IR (KBr) 2961, 2920, 1590, 1576, 1489, 1479, 1425, 1283, 1248, 1229, 1156, 1043, 830, 686 cm -1 S27

28 (4-bromophenyl)(3-methoxyphenyl)Sulfane 4k: Di-(4-bromo)phenyliodium tetrafluoroborate (105.1 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4k [11] (49.7 mg, 84%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 6.83 (dd, J = 7.7, 0.8 Hz, 1H), (m, 1H), 6.73 (ddd, J = 8.3, 2.4, 0.7 Hz, 1H), 3.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.1, 136.2, 135.0, 132.4, 132.2, 130.1, 123.5, 121.1, 116.5, 113.3, IR (KBr) 2950, 2923, 1590, 1576, 1472, 1439, 1425, 1385, 1283, 1247, 1230, 1069, 1043, 1008, 860, 812, 775, 687 cm -1. (3-methoxyphenyl)(4-(trifluoromethyl)phenyl)Sulfan e 4l: Di-(4-trifluoromethyl)phenyliodium tetrafluoroborate (100.8 mg, 0.2 mmol), sodium S- 3-methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4l (40.1 mg, 71%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.50 (d, J = 8.3 Hz, 2H), (m, 3H), 7.05 (dd, J = 7.7, 0.8 Hz, 1H), (m, 1H), 6.92 (ddd, J = 8.3, 2.5, 0.6 Hz, 1H), 3.80 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.3, 142.5, 133.6, 130.4, 128.5, (d, J = 32.7 Hz), (q, J = 3.7 Hz), (m, J = Hz), (d, J = 6.3 Hz), 118.4, 114.5, F NMR (282 MHz, CDCl 3 ) δ IR (KBr) 1607, 1590, 1577, 1480, 1401, 1326, 1283, 1248, 1231, 1166, 1124, 1109, 1090, 1063, 1043, 1014, 828 cm -1. HRMS (EI) Calcd for C 14 H 11 F 3 OS , Found S28

29 (3-methoxyphenyl)(o-tolyl)Sulfane 4m: Di-(2-methyl)phenyliodium tetrafluoroborate (79.2 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4m [12] (31.2 mg, 68%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.26 (d, J = 7.6 Hz, 1H), 7.12 (dd, J = 28.8, 7.7 Hz, 4H), (m, 3H), 3.66 (s, 3H), 2.30 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.0, 140.3, 137.6, 133.4, 133.2, 130.6, 129.9, 128.1, 126.7, 121.5, 114.5, 111.9, 55.2, IR (KBr) 2955, 2935, 1589, 1576, 1475, 1425, 1283, 1247, 1230, 1043, 859, 845, 771, 753, 686 cm -1. Mesityl(3-methoxyphenyl)sulfane 4n: Di-(1,3,5-trimethyl)phenyliodium tetrafluoroborate (90.4 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4n (21.9 mg, 42%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.09 (t, J = 7.9 Hz, 1H), 7.01 (s, 2H), 6.60 (dd, J = 8.3, 1.4 Hz, 1H), (m, 2H), 3.72 (s, 3H), 2.39 (s, 6H), 2.32 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.0, 143.8, 139.9, 139.4, 129.7, 129.4, 126.7, 117.8, 111.1, 109.9, 55.1, 21.7, IR (KBr) 2954, 2922, 1590, 1576, 1559, 1475, 1458, 1438, 1425, 1283, 1247, 1229, 1045, 852, 686 cm -1. HRMS (EI) Calcd for C 16 H 18 OS , Found (3-methoxyphenyl)(3-(trifluoromethyl)phenyl)Sulfane 4o: Di-(3-trifluoromethyl)phenyliodium tetrafluoroborate S29

30 (100.8 mg, 0.2 mmol), sodium S-3-methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4o (41.3 mg, 73%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ 7.53 (s, 1H), 7.39 (tt, J = 15.3, 7.7 Hz, 3H), (m, 1H), (m, 1H), (m, 1H), 6.83 (ddd, J = 8.3, 2.5, 0.7 Hz, 1H), 3.75 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.2, 138.0, 134.8, 133.0, (d, J = 32.5 Hz), 130.3, 129.5, (q, J = 3.9 Hz), (m, J = Hz ), 124.3, (q, J = 3.8 Hz), 117.3, 113.9, F NMR (282 MHz, CDCl 3 ) δ IR (KBr) 2970, 2920, 1458, 1419, 1385, 1325, 1261, 1106, 1090, 1064, 1043, 1016, 802 cm -1. HRMS (EI) Calcd for C 14 H 11 F 3 OS , Found (naphthalen-1-yl)(3-methoxyphenyl)sulfane 4p: Di- (naphthalen-1-yl)iodium tetrafluoroborate (93.6 mg, 0.2 mmol), sodium S- -methoxylphenyl sulfothioate (140.2 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4p [11] (28.2 mg, 53%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.4 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), 7.88 (dd, J = 8.9, 3.8 Hz, 2H), 7.72 (d, J = 7.1 Hz, 1H), 7.53 (dd, J = 6.3, 3.3 Hz, 2H), 7.45 (t, J = 7.7 Hz, 1H), 7.14 (t, J = 7.9 Hz, 1H), 6.73 (dt, J = 8.3, 7.2 Hz, 3H), 3.70 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.0, 138.3, 134.2, 133.7, 132.9, 130.7, 129.8, 129.4, 128.5, 127.0, 126.4, 125.8, 125.6, 121.0, 114.1, 111.7, IR (KBr) 2956, 2933, 1589, 1575, 1503, 1476, 1425, 1381, 1283, 1247, 1230, 1073, 1042, 858, 798, 770, 686 cm -1. S30

31 Phenyl(p-tolyl)sulfane 4q: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S- 4-methylphenyl sulfothioate (135.8 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4q [13] (33.2 mg, 83%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 6H), (m, 1H), (m, 2H), 2.26 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 137.7, 137.2, 132.3, 131.3, 130.1, 129.8, 129.1, 126.4, IR (KBr) 2922, 1582, 1491, 1477, 1439, 1083, 1068, 1024, 1018, 808, 739, 690, 517 cm -1. Phenyl(4-chlorophenyl)Sulfane 4r: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S- 4-chlorophenyl sulfothioate (148.0 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. 4r [14] (33.1 mg, 75%) was obtained through column chromatography (PE) as a colorless oil, R f = 0.5 (PE); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 135.1, 134.6, 132.9, 132.0, 131.3, 129.3, 129.3, IR (KBr) 2924, 1583, 1475, 1458, 1439, 1389, 1095, 1087, 1024, 1012, 816, 739, 704, 690, 509 cm -1. Phenyl(4-(trifluoromethyl)phenyl)sulfane 4s: Diphenyliodium tetrafluoroborate (73.6 mg, 0.2 mmol), sodium S-4-(trifluoromethyl)phenyl sulfothioate (168.1 mg, 0.6 mmol), Eosin Y (2.8 mg, 4*10-3 mmol), Zn(OAc). 2 2H 2 O (4.4 mg, 0.02 mmol), DIPEA (66 μl, 0.4 mmol), MeOH (0.5 ml) was stirred at room temperature for 24 h under the irradiation of 23 W CFL. S31