Ag-Initiated gem-difluoromethylenation of the Nitrogen Center of. Arenediazonium Salts to gem-difluoromethylene Azo Compounds

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Transcript:

Org. Lett. Supporting Information Ag-Initiated gem-difluoromethylenation of the Nitrogen Center of Arenediazonium Salts to gem-difluoromethylene Azo Compounds Haizhen Jiang,*,, Yunrong Chen, Bo Chen, Hui Xu, Wen Wan, Hongmei Deng, Kesen Ma, Shaoxiong Wu,*, and Jian Hao*, Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai, 200444, P. R. China Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, P. R. China Laboratory for Microstructures, Shanghai University, Shanghai, 200444, P. R. China Department of Biology, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada Emory NMR Research Center, Emory University, 201 Dowman Drive, Atlanta, Georgia 30322, United States E-mail: hzjiang@shu.edu.cn; swu@emery.edu; jhao@shu.edu.cn Supporting Information Table of contents 1. General Information. S2 2. Synthesis of Raw Materials S2 - S3 3. General Procedure for gem-difluoromethylene Azo Products 3 S3 - S9 4. General Procedure for Product 3ah in 2 mmol Scale S9 5. Optimization of the Reaction Conditions S10 6. Crystal Information for 3ah S11 - S18 7. Information of ESR S18 - S42 8. 1 H NMR, 13 C NMR and 19 F NMR Spectrums for all Compounds S42 - S87 S1

1. General Information. All solvents were purified by standard method. 1 H NMR spectra were recorded on a 500 MHz. 19 F NMR were recorded on a 470 MHz spectrometer. 13 C NMR spectra were recorded on a 125 MHz spectrometer. 1 H NMR and 13 C NMR chemical shifts were determined relative to internal standard TMS at δ 0.0 and 19 F NMR chemical shifts were determined relative to CFCl 3 as inter standard. Chemical shifts (δ) are reported in ppm, and coupling constants (J) are in Hertz (Hz). The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad. ESR spectra were measured on a Bruker EMX-8/2.7. Infrared spectra (IR) were recorded with KBr pellets. Melting points are uncorrected. High-resolution mass spectrometry (HRMS) was conducted by TOF MS with electron impact (EI) ionization at 70 ev. Silica gel (200 400 mesh) was used for flash column chromatography, and the eluent is a mixture of petroleum ether and ethyl acetate. All reagents were received from commercial sources. Solvents were freshly dried and degassed according to the purification handbook Purification of Laboratory Chemicals before using. 2. Synthesis of Raw Materials 2.1 General procedure for preparation of sodium 1,3-diazolic difluoromethanesulfinate 1 A 100 ml round-bottom flask was charged with 1,3-diazolic difluoromethyl bromide (20 mmol), Na 2 S 2 O 4 (8.67 g, 90%, 45 mmol) and NaHCO 3 (4.04 g, 48 mmol) in CH 3 CN (30 ml) and H 2 O (30 ml). The resulting mixture was stirred for 2 days at room temperature. The mixture was evaporated under vacuum to give a yellow solid. The solid was washed with diethyl ether and extracted with acetone (3 40 ml). The mixture was evaporated under vacuum to give a white solid 1. Sodium benzo-1,3-oxazolic difluoromethane sulfinate (1a) 2.34 g, 46%, White solid, Mp 241 o C(decom.); 1 H NMR (500 MHz, DMSO-d 6 ) δ: 7.84-7.80 (m, 2H), 7.50-7.43 (m, 2H); 19 F NMR (470 MHz, DMSO-d 6 ) δ -115.87; 13 C NMR (125 MHz, DMSO-d 6 ) δ: 156.9 (t, 2 J C-F = 30.3 Hz), 150.9, 140.6, 126.6, 125.5, 121.9 (t, 1 J C-F = 288.4 Hz),120.9, 111.8; IR (KBr, cm -1 ) v: 3067,1613, 1572, 1454, 1239, 1087, 744. Sodium difluoro(5-methylbenzo[d]oxazol-2-yl)methanesulfinate (1b) 2.25 g, 42%, White solid, Mp 211.1-213.7 o C; 1 H NMR (500 MHz, DMSO-d 6 ) δ: 7.66 (d, J = 8.5 Hz, 1H), 7.62 (s, 1H), 7.28 (dd, J = 8.0, 2.0 Hz, 1H), 2.48 (s, 3H); 19 F NMR (470 MHz, DMSO-d 6 ) δ -115.83; 13 C NMR (125 MHz, DMSO-d 6 ) δ: 161.8(t, 2 J C-F = 29.9 Hz), 153.9, 145.6, 139.7, 132.3, S2

126.5 (t, 1 J C-F = 288.3 Hz), 125.3, 115.9, 26.2; IR (KBr, cm -1 ) v: 3065, 1624, 1575, 1452, 1240, 1091, 785, 749. Sodium benzo[d]thiazol-2-yldifluoromethanesulfinate (1c) 1.73 g, 32%, White solid, Mp 205.7-209.1 o C; 1 H NMR (500 MHz, DMSO-d 6 ) δ 8.17(d, J = 7.9 Hz, 1H), 8.12 (d, J = 8.1 Hz, 1H), 7.57 (t, J = 7.7 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H); 19 F NMR (470 MHz, DMSO-d 6 ) δ -107.93; 13 C NMR (125 MHz, DMSO-d 6 ) δ 160.0 (t, J = 27.4 Hz), 152.4, 135.1, 126.5, 123.8 (t, J = 287.0 Hz), 125.8, 123.5, 122.3; (KBr, cm -1 ) v: 3065, 1635,1557,1509, 1458, 1248, 1029, 759, 645 3. General Procedure for gem-difluoromethylene Azo Products 3 A 10 ml round-bottom flask was charged with silver nitrate (0.05 mmol), anhydrous TsOH (0.5 mmol), arenediazonium salts 2 (0.5 mmol), sodium 1,3-diazolic difluoromethanesulfinate 1 (1.5 mmol) and DCM (2 ml) under nitrogen atmosphere. The reaction mixture was stirred at room temperature. After the reaction was completed, the crude product was directly purified by silica gel chromatography (petroleum ether/ethyl acetate = 80/1-60/1), to give desired cross-coupling product 3. 2-(Difluoro((4-fluorophenyl)diazenyl)methyl)benzo[d]oxazole (3aa) 117.8 mg, 81% yield, light yellow solid, Mp 72-75 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.84 (d, J = 7.5 Hz, 1H), 7.76 (td, J = 8.0, 1.5 Hz, 1H), 7.62 (d, J = 8.0 Hz,1H), 7.59-7.55 (m, 1H), 7.48-7.41 (m, 2H), 7.23-7.21 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.01, -119.86 (m); 13 C NMR (125 MHz, CDCl 3 ) δ:161.8 (d, 1 J C-F = 262.5 Hz), 154.9 (t, 2 J C-F = 37.8 Hz), 150.9, 139.9, 138.5 (d, 3 J C-F = 6.5 Hz), 136.3 (d, 3 J C-F = 8.8 Hz), 127.1, 125.5, 124.5, 121.5, 118.3, 117.6 (d, 2 J C-F = 19.3 Hz), 117.1 (t, 1 J C-F = 248.6 Hz), 111.4; IR (KBr, cm -1 ): v:3068, 1593, 1509, 1453, 1306, 1235, 1118, 850, 747. HRMS (EI TOF) calcd for (M+) C 14 H 8 F 3 N 3 O: 291.0619, found: 291.0623. Ethyl 2-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzoate (3ab) 165.6 mg, 96% yield, light yellow solid, Mp 94-97 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.78 (d, J = 7.7 Hz, 1H), 7.73 (d, J = 7.7 Hz, 1H), 7.55 (d, J = 7.7 Hz, 1H), 7.49 (s, 3H), 7.40-7.33 (m, 2H), 4.00 (qd, J = 7.1, 3.4 Hz, 2H), 1.11 (td, J = 7.1, 3.7 Hz, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.20; 13 C NMR (125 MHz, CDCl 3 ) δ: 166.1, 154.7 (t, 2 J C-F = 37.5 Hz), 150.8, 148.8, 139.9, 132.8, 131.9, 131.4, 129.9, 127.0, 125.4, 121.3, 117.6, 117.1 (t, 1 J C-F = 247.5 Hz), 111.4, 61.7, 13.8; IR (KBr, cm -1 ):v: 3010, 1736, 1691, 1550, 1456, 1285, 1093, 1019, 751; HRMS (EI TOF) calcd for (M+) C 17 H 13 F 2 N 3 O 3 : 345.0925, found: 345.0929. S3

Ethyl 4-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzoate (3ac) 163.9 mg, 95% yield, light brown solid, Mp 101-104 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 8.16 (d, J = 8.5 Hz, 2H), 7.91 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8.5 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.48-7.41 (m, 2H), 4.40 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.23; 13 C NMR (125 MHz, CDCl 3 ) δ: 165.3, 154.7 (t, 2 J C-F = 37.5 Hz), 152.5, 150.8, 139.9, 135.1, 130.6, 127.1, 125.5, 123.8, 121.5, 117.0 (t, 1 J C-F = 248.8 Hz), 111.5, 61.6, 14.2; IR (KBr, cm -1 ) v: 3012, 1717, 1684, 1605, 1456, 1279, 1099, 1041, 863, 750; HRMS (EI TOF) calcd for (M+) C 17 H 13 F 2 N 3 O 3 : 345.0925, found: 345.0934. Ethyl 3-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzoate (3ad) 120.8 mg, 70% yield, light brown solid, Mp 171-173 o C; 1 H NMR (500 MHz, CDCl 3 ) δ 8.52 (s, 1H), 8.26 (d, J = 7.5 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.63 (d, J = 8.5 Hz, 1H), 7.60 (t, J = 8.0 Hz, 1H), 7.50-7.42 (m, 2H), 4.40 (q, J = 7.0 Hz, 2H), 1.40 (t, J = 7.0 Hz, 3H). 19 F NMR (470 MHz, CDCl 3 ) δ -90.13. 13 C NMR (125 MHz, CDCl 3 ) δ 165.3, 154.9 (t, 2 J C-F = 38.3 Hz), 150.9, 150.3, 139.9, 134.8, 132.1, 129.5, 127.3, 127.1, 125.8, 125.5, 121.6, 117.1 (t, 1 J C-F = 248.1 Hz), 111.5, 61.6, 14.3. IR (KBr, cm -1 ):v: 3014, 1720, 1684, 1554, 1461, 1277, 1098, 1025, 751; HRMS (EI TOF) calcd for (M+) C 17 H 13 F 2 N 3 O 3 : 345.0925, found: 345.0931. 1-(4-((Benzo[d]oxazol-2-yldifluoromethyl)diazenyl)phenyl)ethan-1-one (3ae) 119.7 mg, 76% yield, light yellow solid, Mp 119-120 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 8.05 (d, J = 8.0 Hz, 2H), 7.91 (d, J = 8.0 Hz, 2H), 7.81 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.46-7.39 (m, 2H), 2.62 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.19; 13 C NMR (125 MHz, CDCl 3 ) δ: 197.0, 154.6 (t, 2 J C-F = 37.5 Hz), 152.4, 150.9, 140.8, 139.9, 129.3, 127.2, 125.5, 124.2, 121.5, 117.0 (t, 1 J C-F = 248.8 Hz), 111.5, 26.9; IR (KBr, cm -1 ): v: 3088, 1687, 1608, 1450, 1359, 1258, 1117, 1049, 855, 756; HRMS (EI TOF) calcd for (M+) C 16 H 11 F 2 N 3 O 2 : 315.0819, found: 315.0812. (2-((Benzo[d]oxazol-2-yldifluoromethyl)diazenyl)phenyl)(phenyl)methanone (3af) 175.3 mg, 93% yield, yellow solid, Mp 107-111 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.85-7.83 (m, 1H), 7.65-7.61 (m, 3H), 7.50-7.48 (m, 1H), 7.39-7.32 (m, 5H), 7.23-7.20 (m, 1H), 7.07-7.05 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.59; 13 C NMR (125 MHz, CDCl 3 ) δ 195.3, 154.5 (t, 2 J C-F = 38.1 Hz), 150.7, 147.4, 140.7, 139.7, 137.0, 134.5, 133.2, 130.9, 129.2, 128.8, 128.2, 126.8, 125.2, 121.5, 117.8, 117.2 (t, 1 J C-F = 247.5 Hz), 111.5; IR (KBr, cm -1 ): v: 3062, 1670, 1511, 1244, 1120, 1035, 757, 690; HRMS (EI TOF) calcd for (M+) C 21 H 13 F 2 N 3 O 2 : 377.0976, found: 377.0958. 4-((Benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzonitrile (3ag) S4

101.3 mg, 68% yield, light yellow solid, Mp165-166 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.97 (d, J = 8.0 Hz, 2H), 7.83 (t, J = 8.0 Hz, 3H), 7.62 (d, J = 8.0 Hz, 1H), 7.50-7.42 (m, 2H); 19 F NMR (471 MHz, CDCl 3 ) δ: -90.44; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.3 (t, 2 J C-F = 25.0 Hz), 151.9, 150.9, 139.9, 133.4, 127.3, 125.6, 124.5, 121.6, 117.6, 117.2, 116.9 (t, 1 J C-F = 250.0 Hz), 115.0; IR (KBr, cm -1 ): v: 3094, 2227, 1611, 1521, 1303, 1121, 853, 752; HRMS (EI TOF) calcd for (M+) C 15 H 8 F 2 N 4 O: 298.0666, found: 298.0661. 2-(Difluoro((4-nitrophenyl)diazenyl)methyl)benzo[d]oxazole (3ah) 87.5 mg, 55% yield, yellow solid, Mp177-179 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 8.38 (d, J = 8.0 Hz, 2H), 8.05 (d, J = 8.0 Hz, 2H), 7.86 (d, J = 8.0 Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.52-7.44 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.51; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.3 (t, 2 J C-F = 37.6 Hz), 153.1, 150.9, 150.6, 139.9, 127.3, 125.7, 124.8, 121.6, 116.8 (t, 1 J C-F = 250.0 Hz), 111.5; IR (KBr, cm -1 ): v: 3069, 1607, 1528, 1116, 1044, 807, 754; HRMS (EI TOF) calcd for (M+) C 14 H 8 F 2 N 4 O 3 : 318.0564, found: 318.0553. 2-(Difluoro((4-(trifluoromethyl)phenyl)diazenyl)methyl)benzo[d]oxazole (3ai) 93.8 mg, 55% yield, brown solid, Mp121-124 o C; 1 H NMR (500 MHz, CDCl 3 ) δ:7.99 (d, J = 8.0 Hz, 2H), 7.86 (d, J = 7.8 Hz, 1H), 7.78 (d, J = 8.0 Hz, 2H), 7.63 (d, J = 8.0 Hz, 1H), 7.50-7.42 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -63.10, -90.41; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.1 (t, 2 J C-F = 37.8 Hz), 151.5, 150.4, 139.4, 134.7 (q, 2 J C-F = 33.0 Hz), 126.7, 126.1 (q, 3 J C-F = 3.7 Hz), 125.1, 124.0, 122.9 (q, 1 J C-F = 270.9 Hz) 121.1, 116.5 (t, 1 J C-F = 250.6 Hz), 111.1; IR (KBr, cm -1 ): v: 3068, 1687, 1611, 1454, 1325, 1172, 1112, 855, 744; HRMS (EI TOF) calcd for (M+) C 15 H 8 F 5 N 3 O: 341.0588, found: 341.0571. 2-(Difluoro((2-fluorophenyl)diazenyl)methyl)benzo[d]oxazole (3aj) 75.7 mg, 52% yield, light yellow solid, Mp 50-52 o C; 1 H NMR (500 MHz, CDCl 3 ) δ 7.94 (dd, J = 9.0, 5.5 Hz, 2H), 7.85 (d, J = 7.5 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.49-7.43 (m, 2H), 7.18 (t, J = 8.5 Hz, 2H). 19 F NMR (470 MHz, CDCl 3 ) δ -89.89, -103.22-103.28 (m). 13 C NMR (125 MHz, CDCl 3 ) δ 166.3 (d, 1 J C-F = 255.8 Hz), 155.1 (t, 2 J C-F = 38.3 Hz), 150.9, 146.9 146.9, 139.9, 127.0, 126.7, 126.7, 125.5, 121.5, 117.1 (t, 1 J C-F = 248.5 Hz), 116.6 (d, 2 J C-F = 23.2 Hz), 111.4. IR (KBr, cm -1 ): v: 3072, 1603, 1483, 1307, 1133, 1077, 833, 756; HRMS (EI TOF) calcd for (M+) C 14 H 8 F 3 N 3 O: 291.0619, found: 291.0623. 2-(((2,4-Difluorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3ak) 114.3 mg, 74% yield, yellow solid, Mp 58-59 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.82 (d, J = 7.9 Hz, 1H), 7.74-7.68 (m, 2H), 7.61-7.59 (m, 1H),7.45-7.40 (m, 2H),7.30-7.28 (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.07, -127.18, -134.17; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.7 (t, 2 J C-F = 38.1 Hz), 154.6 (dd, 1 J C-F = 245.0, 3 J C-F = 13.7 Hz), 150.8 (dd, 1 J C-F = 251.3 Hz, 3 J C-F = 13.7 Hz), 151.7, 146.7 (t, J = 4.1 Hz), 139.9, 127.1, 125.5, 123.7 (dd, J = 2.5, 7.0 Hz), 121.4, 117.8 (d, 2 J C-F = 18.7 Hz), 117.0 (t, S5

1 J C-F = 249.9 Hz), 111.4, 111.0 (d, 2 J C-F = 18.7 Hz); IR (KBr, cm -1 ): v: 3062, 1609, 1516, 1282, 1186, 1063, 840, 754; HRMS (EI TOF) calcd for (M+) C 14 H 7 F 4 N 3 O: 309.0525, found: 309.0520. 2-(((4-Chlorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3al) 116.7 mg, 76% yield, yellow solid, Mp124-126 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.84 (t, J = 9.1 Hz, 3H), 7.62 (d, J = 8.0 Hz, 1H), 7.48-7.42 (m, 4H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.98; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.9 (t, 2 J C-F = 37.8 Hz), 150.9, 148.7, 140.7, 139.9, 129.7, 127.1, 125.5, 125.4, 121.5, 117.1 (t, 1 J C-F = 249.3 Hz), 111.5; IR (KBr, cm -1 ): v: 3092, 1686, 1511, 1401, 1181, 836, 749; HRMS (EI TOF) calcd for (M+) C 14 H 8 ClF 2 N 3 O: 307.0324, found: 307.0318. 2-(((2-Chlorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3am) 101.3 mg, 66% yield, pale yellow solid, Mp 52-53 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.81 (d, J = 7.2 Hz, 1H), 7.63-7.61 (m, 1H), 7.57-7.55 (m,1h), 7.41-7.36 (m, 4H), 7.23-7.21 (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.85; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.8 (t, 2 J C-F = 38.0 Hz), 150.9, 146.4,139.9, 137.7, 135.1, 131.1, 127.4, 127.1, 125.4, 121.4, 117.6, 117.4 (t, 1 J C-F = 250.2 Hz), 111.3; IR (KBr, cm -1 ): v: 3092, 1694, 1512, 1459, 1302, 1131, 1039, 810, 756; HRMS (EI TOF) calcd for (M+) C 14 H 8 ClF 2 N 3 O: 307.0324, found: 307.0321. 2-(((4-Bromophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3an) 128.5 mg, 73% yield, brown solid, Mp 146-148 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.84 (d, J = 7.5 Hz, 1H), 7.74 (d, J = 8.8 Hz, 2H), 7.63-7.60 (m, 3H), 7.47-7.40 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.95; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.9(t, 2 J C-F = 38.3 Hz), 150.9, 149.0, 139.9, 132.9, 129.4, 127.8, 127.1, 125.5, 121.5, 117.1 (t, 1 J C-F = 249.5 Hz), 111.5; IR (KBr, cm -1 ): v: 3090, 1683 1504, 1400, 1301, 1183, 1107, 840, 748; HRMS (EI TOF) calcd for (M+) C 14 H 8 BrF 2 N 3 O: 350.9819, found: 350.9825. 2-(((2-Bromophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3ao) 129.9 mg, 74% yield, light yellow solid, Mp 46-47 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.84 7.83 (m, 1H), 7.70-7.65 (m, 2H), 7.60 (d, J = 7.8 Hz, 1H), 7.46-7.38 (m, 4H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.18; 13 C NMR (125 MHz, CDCl 3 ) δ:154.9 (t, 2 J C-F = 37.8 Hz), 151.0, 147.5, 140.0, 135.1, 134.3, 128.1, 127.0, 125.4, 121.4, 117.9, 117.3 (t, 1 J C-F = 249.2 Hz), 111.3; IR (KBr, cm -1 ): v: 3069, 1613, 1574, 1456, 1304, 1133, 1043, 809, 754; HRMS (EI TOF) calcd for (M+) C 14 H 8 BrF 2 N 3 O: 350.9819, found: 350.9822. 2-(Difluoro((4-iodophenyl)diazenyl)methyl)benzo[d]oxazole (3ap) 109.7 mg, 55% yield, yellow solid, Mp156-160 o C; 1 H NMR (500 MHz,CDCl 3 ) δ: 7.87-7.84 (m, 3H), 7.63-7.58 (m, 3H), 7.49-7.42 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.05; 13 C NMR (125 MHz, S6

CDCl 3 ) δ: 154.9 (t, 2 J C-F = 38.1 Hz), 150.9, 149.6, 139.9, 138.8, 127.1, 125.5, 125.5, 121.5, 117.1 (t, 1 J C-F = 249.6 Hz), 111.5, 102.3; IR (KBr, cm -1 ): v: 3085, 1571, 1502, 1301, 1107, 1042, 837, 750, 506; HRMS (EI TOF) calcd for (M+) C 14 H 8 F 2 IN 3 O: 398.9680, found: 398.9674. 2-(Difluoro((2-iodophenyl)diazenyl)methyl)benzo[d]oxazole (3aq) 111.7 mg, 56% yield, colorless solid, Mp47-50 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.95 (dd, J = 7.9, 1.0 Hz, 1H), 7.86-7.84 (m, 1H), 7.66-7.61 (m, 2H), 7.47-7.40 (m, 3H), 7.24-7.22 (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.03; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.9 (t, 2 J C-F = 38.3 Hz), 151.1, 149.2, 140.4, 140.1, 135.3, 129.0, 126.9, 125.3, 121.4, 117.5, 117.2 (t, 1 J C-F = 248.3 Hz), 111.4, 104.8; IR (KBr, cm -1 ): v: 3064, 1571, 1450, 1361, 1307, 1162,1067, 757, 541; HRMS (EI TOF) calcd for (M+) C 14 H 8 F 2 IN 3 O: 398.9680, found: 398.9674. 2-(((4-Bromo-2-chlorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3ar) 152.5 mg, 79% yield, light yellow solid, Mp113-114 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.83 (d, J = 7.2 Hz, 1H), 7.64 (d, J = 2.0 Hz, 1H), 7.60-7.56 (m, 2H), 7.46-7.44 (m, 2H), 7.40 (td, J = 7.7, 1.2 Hz, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.01; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.6 (t, 2 J C-F = 38.0 Hz), 150.9, 145.3, 139.9, 138.7, 133.8, 130.9, 129.4, 127.1, 125.5, 121.5, 118.7, 117.2 (t, 1 J C-F = 250.2 Hz), 111.4; IR (KBr, cm -1 ):v: 3078, 1608, 1567, 1508, 1381, 1300, 1112, 1040, 862, 823, 746, 555; HRMS (EI TOF) calcd for (M+) C 14 H 7 BrClF 2 N 3 O: 384.9429, found: 384.9425. 2-(Difluoro((4'-fluoro-[1,1'-biphenyl]-4-yl)diazenyl)methyl)benzo[d]oxazole (3as) 126.6 mg, 69% yield, light yellow solid, Mp 148-150 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.95 (d, J = 8.5 Hz, 2H), 7.86 (d, J = 8.4 Hz, 1H), 7.66 (d, J = 8.5 Hz, 2H), 7.63 (d, J = 7.7 Hz, 1H), 7.62-7.57 (m, 2H), 7.48-7.44 (m, 2H), 7.15 (t, J = 8.6 Hz, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.67, -113.19--113.25 (m); 13 C NMR (125 MHz, CDCl 3 ) δ: 162.7 (d, 1 J = 250.0 Hz), 154.8 (t, 2 J C-F = 38.6 Hz), 150.4, 148.9, 145.5, 139.5, 135.0, 128.5 (d, 3 J = 8.3 Hz), 127.3, 126.9, 125.2, 124.4, 121.3, 116.8 (t, 1 J C-F = 248.5 Hz), 115.5 (d, 2 J = 21.7 Hz), 111.7; IR (KBr, cm -1 ): v: 3069, 1600, 1497, 1299, 1175, 1105, 823, 746; HRMS (EI TOF) calcd for (M+) C 20 H 12 F 3 N 3 O: 367.0932, found: 367.0930. 2-(Difluoro(phenyldiazenyl)methyl)benzo[d]oxazole (3at) 61.4 mg, 45% yield, light brown solid, Mp 50-55 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.85-7.83 (m, 3H), 7.59-7.57 (m, 1H), 7.56-7.49 (m, 1H), 7.47-7.41 (m, 3H), 7.42-7.36 (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.83; 13 C NMR (125 MHz, CDCl 3 ) δ: 155.2 (t, 2 J C-F = 38.4 Hz), 150.9, 150.3, 140.0, 134.3, 129.3, 127.0, 125.4, 124.1, 121.5, 117.3 (t, 1 J C-F = 248.6 Hz), 111.4; IR (KBr, cm -1 ): v: 3063, 1612, 1512, 1452, 1304, 1119, 808, 751; HRMS (EI TOF) calcd for (M+) C 14 H 9 F 2 N 3 O: 273.0714, found: 273.0711. 2-(Difluoro(p-tolyldiazenyl)methyl)benzo[d]oxazole (3au) S7

109.1 mg, 76% yield, brown solid, Mp 176-180 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.79 (d, J = 7.7 Hz, 1H), 7.69 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 8.1 Hz, 1H), 7.40-7.33 (m, 2H), 7.19 (d, J = 8.1 Hz, 2H), 2.33 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.32; 13 C NMR (125 MHz, CDCl 3 ) δ: 155.4 (t, 2 J C-F = 38.8 Hz), 150.8, 148.5, 145.7, 139.9, 130.0, 127.0, 125.4, 124.2, 121.3, 117.5 (t, 1 J C-F = 247.7 Hz), 111.4, 21.6; IR (KBr, cm -1 ): v: 3063, 2920, 1682, 1556, 1460, 1278, 1147, 1107, 824, 744; HRMS (EI TOF) calcd for (M+) C 15 H 11 F 2 N 3 O: 287.0870, found: 287.0873. 2-(Difluoro((4-methoxyphenyl)diazenyl)methyl)benzo[d]oxazole (3av) 57.6 mg, 38% yield, brown solid, Mp 81-83 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.87-7.84 (m, 3H), 7.60 (d, J = 8.0 Hz, 1H), 7.46-7.42 (m, 2H), 6.94 (d, J = 8.0 Hz, 2H), 3.83 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.13; 13 C NMR (125 MHz, CDCl 3 ) δ: 164.7, 155.7 (t, 2 J C-F = 38.8 Hz), 150.9, 144.7, 140.0, 126.9, 126.7, 125.3, 121.5, 117.4 (t, 1 J C-F = 245.5 Hz), 114.6, 111.4, 55.8; IR (KBr, cm -1 ): v: 3053, 2845, 1684, 1598, 1506, 1262, 1105, 1045, 837, 746; HRMS (EI TOF) calcd for (M+) C 15 H 11 F 2 N 3 O 2 : 303.0819, found: 303.0818. 2-(Difluoro((2-Chloro-3-pyridinyl)diazenyl)methyl)benzo[d]oxazole (3aw) 24.1 mg, 21% yield, brown solid, Mp 77.1 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 8.61 (dd, J = 4.7, 1.9 Hz, 1H), 8.02 (dd, J = 8.0, 1.9 Hz, 1H), 7.85 (dd, J = 8.0, 1.9 Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.49 (td, J = 7.8, 1.3 Hz, 1H), 7.44 (td, J = 7.8, 1.2 Hz, 1H), 7.40 (dd, J = 8.0, 4.7 Hz, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.39; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.4, 154.3 (t, 2 J C-F = 37.6 Hz), 150.9, 142.9, 139.9, 139.8, 127.3, 126.2, 125.6, 123.3, 121.6, 117.0 (t, 1 J C-F = 252.0 Hz), 111.4; IR (KBr, cm -1 ): v: 3042, 1790, 1614, 1566, 1511, 1414, 1303, 1125, 1050, 814, 744, 697; HRMS (EI TOF) calcd for (M+) C 13 H 7 ClF 2 N 4 O: 308.0276, found: 308.0281. Methyl-3-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)thiophene-2-carboxylate (3ax) 110.7 mg, 85% yield, brown solid, Mp 150.2 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.90 (d, J = 7.3 Hz, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.54 7.45 (m, 4H), 3.34 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.09; 13 C NMR (125 MHz, CDCl 3 ) δ:161.2, 155.2 (t, 2 J C-F = 37.8 Hz), 152.0, 151.0, 140.0, 138.0, 130.5, 126.9, 125.4, 121.5, 118.0 (t, 1 J C-F = 248.2 Hz), 117.8, 111.4, 52.2; IR (KBr, cm -1 ): v: 3110, 1617, 1531, 1442, 1259, 1184, 1119, 1050, 789, 749; HRMS (EI TOF) calcd for (M+) C 14 H 9 F 2 N 3 O 3 S: 337.0333, found: 337.0330. 2-(Difluoro((1-methyl-4,5-dihydro-1H-pyrazol-3-yl)diazenyl)methyl)benzo[d]oxazole (3ay) 65.7 mg, 66 % yield, brown solid, Mp 115.3 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.83 (d, J = 7.6 Hz, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.47-7.41 (m, 3H), 6.70 (d, J = 2.5 Hz, 1H), 3.99 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: -89.35; 13 C NMR (125 MHz, CDCl 3 ) δ: 161.4, 155.1 (t, 2 J C-F = 38.5 Hz), 150.9, 139.9, S8

132.6, 126.9, 125.3, 121.4, 117.5 (t, 1 J C-F = 247.5 Hz), 111.5, 97.7, 40.0; IR (KBr, cm -1 ): v: 3125, 1619, 1511, 1449, 1365, 1137, 1076, 846, 756; HRMS (EI TOF) calcd for (M+) C 12 H 9 F 2 N 5 O: 277.0775, found: 277.0772. Ethyl 4-((difluoro(5-methylbenzo[d]oxazol-2-yl)methyl)diazenyl)benzoate (3bc) 170.6 mg, 95%, Yellow solid, mp:81-83, 1 H NMR (500 MHz, CDCl 3 ) δ 8.19 (d, J = 8.7 Hz, 2H), 7.94 (d, J = 8.7 Hz, 2H), 7.64 (s, 1H), 7.51 (d, J = 8.4 Hz, 1H), 7.30 (d, J = 10.5 Hz, 1H), 4.43 (q, J = 7.1 Hz, 2H), 2.51 (s, 3H), 1.43 (td, J = 7.1, 1.0 Hz, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ -90.33; 13 C NMR (125 MHz, CDCl 3 ) δ 165.4, 154.7 (t, 2 J C-F = 37.8 Hz), 152.5, 149.2, 140.1, 135.6, 135.0, 130.6, 128.4, 123.8, 121.2, 117.0 (t, 1 J C-F = 253.2 Hz), 110.8, 61.6, 21.5, 14.3; IR (KBr, cm -1 ): v 3059, 2991, 1713, 1616, 1573, 1451, 1261, 1082, 914, 774, 748. HRMS (EI TOF) calcd for (M+) C 18 H 15 F 2 N 3 O 3 : 359.1081, found: 359.1076 (E)-2-(((4-Chlorophenyl)diazenyl)difluoromethyl)benzo[d]thiazole (3cl) 119.5 mg, 74%, Yellow solid, mp:136-138 ; 1 H NMR (500 MHz, CDCl 3 ) δ 8.17 (d, J = 8.4 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 8.8 Hz, 2H), 7.58 (td, J = 8.4, 1.1 Hz, 1H), 7.50 (d, J = 7.0 Hz, 1H), 7.48 (d, J = 8.8 Hz, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ -85.04; 13 C NMR (125 MHz, CDCl 3 ) δ 159.6 (t, 2 J C-F = 37.8 Hz), 152.7, 149.0, 140.3, 135.3, 129.7, 127.0, 126.9, 125.3, 124.8, 121.9, 119.1 (t, 1 J C-F = 250.5 Hz); IR (KBr, cm -1 ): v: 3081, 1686, 1511, 1401, 1181, 836, 749; HRMS (EI TOF) calcd for (M+) C 14 H 8 ClF 2 N 3 S: 323.0096, found: 323.0091 4. General Procedure for Product 3ah in 2 mmol Scale A 10 ml round-bottom flask was charged with silver nitrate (0.2 mmol, 33.8 mg), anhydrous TsOH (2.0 mmol, 344.4 mg), p-nitrophenyl diazonium tetrafluoroborates 2c (2.0 mmol, 546 mg), sodium 1,3-oxazolic difluoromethanesulfinate 1 (6.0 mmol, 1530 mg) and DCM (8 ml) under nitrogen atmosphere. The reaction mixture was stirred at room temperature. After the reaction was completed, the crude product was directly purified by silica gel chromatography (petroleum ether/ethyl acetate = 60/1), to give desired product 3ah. 2-(Difluoro((4-nitrophenyl)diazenyl)methyl)benzo[d]oxazole (3ah) 362.5 mg, 57% yield, yellow solid, Mp177-179 o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 8.38 (d, J = 8.0 Hz, 2H), 8.05 (d, J = 8.0 Hz, 2H), 7.86 (d, J = 8.0 Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.52-7.44 (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: -90.51; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.3 (t, 2 J C-F = 37.6 Hz), 153.1, 150.9, 150.6, 139.9, 127.3, 125.7, 124.8, 121.6, 116.8 (t, 1 J C-F = 250.0 Hz), 111.5; IR (KBr, cm -1 ): v: 3069, 1607, 1528, 1116, 1044, 807, 754 S9

5. Optimization of the Reaction Conditions Table S1 Optimization of the reaction conditions entry promoter (equiv) solvent TBHP (equi) additive (equiv) 3aa yield a (%) 1 CuI (0.5) DMF 6.0 TsOH (1.0) 14 19 CuI (0.5) THF 6.0 TsOH (1.0) 16 20 CuI (0.5) DMSO 6.0 TsOH (1.0) 0 21 CuI (0.5) Dioxane 6.0 TsOH (1.0) 41 22 CuI (0.5) NMP 6.0 TsOH (1.0) 0 23 CuI (0.5) CH 3 CN 6.0 TsOH (1.0) 0 24 CuI (0.5) Dichloroethane 6.0 TsOH (1.0) 45 2 CuI (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 69 3 AgNO 3 (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 85 25 AlCl 3 (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 35 26 ZnCl 2 (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 41 27 CuSCN (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 74 28 CuSO 4 (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 68 4 AgOAc (0.5) CH 2 Cl 2 6.0 TsOH(1.0) 80 29 AgNO 3 (0.5) CH 2 Cl 2 6.0 HCl(1.0) 77 30 AgNO 3 (0.5) CH 2 Cl 2 6.0 CH 3 COOH(1.0) 51 31 AgNO 3 (0.5) CH 2 Cl 2 6.0 TFA(1.0) 82 32 AgNO 3 (0.5) CH 2 Cl 2 6.0 PhCOOH(1.0) 42 33 AgNO 3 (0.1) CH 2 Cl 2 6.0 TsOH (0.1) 71 34 AgNO 3 (0.1) CH 2 Cl 2 2.0 TsOH(0.5) 81 35 AgNO 3 (0.1) CH 2 Cl 2 0.25 TsOH(0.5) 70 5 AgNO 3 (0.5) CH 2 Cl 2 0.5 TsOH(1.0) 85 6 AgNO 3 (0.5) CH 2 Cl 2 0.5 / 65 7 AgNO 3 (0.1) CH 2 Cl 2 / TsOH(1.0) 86 8 AgNO 3 (0.1) CH 2 Cl 2 / TsOH(0.5) 63 9 AgNO 3 (0.1) CH 2 Cl 2 / TsOH (0.1) 61 10 AgNO 3 (0.2) CH 2 Cl 2 / TsOH (0.5) 69 11 AgNO 3 (0.1) CH 2 Cl 2 / / 46 12 / CH 2 Cl 2 / / 44 13 / CH 2 Cl 2 0.5 TsOH(1.0) 71 14 / CH 2 Cl 2 0.5 TsOH(0.5) 82 15 / CH 2 Cl 2 0.5 / 68 16 / CH 2 Cl 2 0.25 / 76 17 b AgNO 3 (0.1) CH 2 Cl 2 / TsOH (1.0) 36 18 c AgNO 3 (0.1) CH 2 Cl 2 / TsOH (1.0) 45 36 FeCl 3 (0.1) CH 2 Cl 2 / TsOH (1.0) 62 37 AgNO 3 (0.1) CH 2 Cl 2 / TsOH.H 2 O (1.0) 72 a 19 F NMR yield using benzotrifluoride as an internal standard, reactions were carried out with molar ratio 3:1 of 1a:2a in 2 ml solvent at rt for 8 hr. b at 70 o C. c at 0 o C. S10

6. Crystal Information for 3ah (CCDC:1534233) 1) Crystal data and structure refinement for cd17083 Identification code cd17083 Empirical formula C14 H8 F2 N4 O3 Formula weight 318.24 Temperature 293(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group C 2/c Unit cell dimensions a = 21.698(5) Å = 90. b = 4.6497(11) Å = 103.715(6). c = 27.179(6) Å = 90. Volume 2663.9(11) Å 3 Z 8 Density (calculated) 1.587 Mg/m 3 Absorption coefficient 0.134 mm -1 F(000) 1296 Crystal size 0.200 x 0.110 x 0.040 mm 3 Theta range for data collection 1.542 to 24.998. Index ranges -23<=h<=25, -5<=k<=5, -32<=l<=28 Reflections collected 6851 Independent reflections 2340 [R(int) = 0.0499] Completeness to theta = 25.242 96.3 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7456 and 0.6028 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2340 / 0 / 208 Goodness-of-fit on F 2 1.234 Final R indices [I>2sigma(I)] R1 = 0.0814, wr2 = 0.1613 R indices (all data) R1 = 0.1066, wr2 = 0.1723 Extinction coefficient n/a Largest diff. peak and hole 0.209 and -0.222 e.å -3 2) Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for cd17083. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) S11

F(1) 3341(1) 13516(5) 1833(1) 55(1) F(2) 4356(1) 13947(5) 1960(1) 62(1) N(1) 4348(1) 9852(7) 1228(1) 42(1) N(2) 4018(1) 10149(7) 2332(1) 39(1) N(3) 3531(1) 9364(6) 2440(1) 39(1) N(4) 3737(2) 1356(8) 4014(1) 56(1) O(1) 3334(1) 8950(6) 1210(1) 50(1) O(2) 4252(2) 526(9) 4236(1) 90(1) O(3) 3248(2) 551(9) 4105(1) 89(1) C(1) 3493(2) 7405(8) 823(1) 40(1) C(2) 3122(2) 5549(11) 489(2) 66(1) C(3) 3419(2) 4279(10) 149(2) 67(1) C(4) 4039(2) 4817(10) 156(2) 60(1) C(5) 4404(2) 6669(10) 494(2) 56(1) C(6) 4113(2) 7948(8) 835(1) 39(1) C(7) 3875(2) 10317(8) 1423(1) 38(1) C(8) 3880(2) 12018(8) 1885(1) 41(1) C(9) 3633(2) 7365(7) 2856(1) 33(1) C(10) 4214(2) 6284(8) 3102(1) 41(1) C(11) 4252(2) 4304(9) 3480(1) 46(1) C(12) 3700(2) 3525(8) 3610(1) 40(1) C(13) 3120(2) 4568(9) 3371(2) 49(1) C(14) 3085(2) 6526(8) 2988(1) 43(1) 3). Bond lengths [Å] and angles [ ] for cd17083. F(1)-C(8) 1.340(4) F(2)-C(8) 1.346(4) N(1)-C(7) 1.280(4) N(1)-C(6) 1.389(5) N(2)-N(3) 1.218(4) N(2)-C(8) 1.466(5) N(3)-C(9) 1.439(4) N(4)-O(2) 1.202(4) N(4)-O(3) 1.204(5) N(4)-C(12) 1.480(5) O(1)-C(7) 1.340(4) O(1)-C(1) 1.383(4) C(1)-C(6) 1.360(5) S12

C(1)-C(2) 1.367(5) C(2)-C(3) 1.379(6) C(2)-H(2) 0.9300 C(3)-C(4) 1.364(6) C(3)-H(3) 0.9300 C(4)-C(5) 1.366(6) C(4)-H(4) 0.9300 C(5)-C(6) 1.375(5) C(5)-H(5) 0.9300 C(7)-C(8) 1.481(5) C(9)-C(10) 1.376(5) C(9)-C(14) 1.377(5) C(10)-C(11) 1.368(5) C(10)-H(10) 0.9300 C(11)-C(12) 1.374(5) C(11)-H(11) 0.9300 C(12)-C(13) 1.362(5) C(13)-C(14) 1.371(5) C(13)-H(13) 0.9300 C(14)-H(14) 0.9300 C(7)-N(1)-C(6) 103.9(3) N(3)-N(2)-C(8) 111.1(3) N(2)-N(3)-C(9) 113.7(3) O(2)-N(4)-O(3) 123.9(4) O(2)-N(4)-C(12) 118.1(4) O(3)-N(4)-C(12) 118.0(4) C(7)-O(1)-C(1) 103.0(3) C(6)-C(1)-C(2) 123.8(4) C(6)-C(1)-O(1) 108.0(3) C(2)-C(1)-O(1) 128.2(4) C(1)-C(2)-C(3) 114.8(4) C(1)-C(2)-H(2) 122.6 C(3)-C(2)-H(2) 122.6 C(4)-C(3)-C(2) 122.0(4) C(4)-C(3)-H(3) 119.0 C(2)-C(3)-H(3) 119.0 C(3)-C(4)-C(5) 122.4(4) S13

C(3)-C(4)-H(4) 118.8 C(5)-C(4)-H(4) 118.8 C(4)-C(5)-C(6) 116.1(4) C(4)-C(5)-H(5) 121.9 C(6)-C(5)-H(5) 121.9 C(1)-C(6)-C(5) 120.9(4) C(1)-C(6)-N(1) 108.6(3) C(5)-C(6)-N(1) 130.6(4) N(1)-C(7)-O(1) 116.6(3) N(1)-C(7)-C(8) 126.5(3) O(1)-C(7)-C(8) 116.7(3) F(1)-C(8)-F(2) 106.7(3) F(1)-C(8)-N(2) 113.4(3) F(2)-C(8)-N(2) 105.7(3) F(1)-C(8)-C(7) 110.9(3) F(2)-C(8)-C(7) 109.6(3) N(2)-C(8)-C(7) 110.2(3) C(10)-C(9)-C(14) 121.3(3) C(10)-C(9)-N(3) 124.7(3) C(14)-C(9)-N(3) 114.0(3) C(11)-C(10)-C(9) 119.6(3) C(11)-C(10)-H(10) 120.2 C(9)-C(10)-H(10) 120.2 C(10)-C(11)-C(12) 118.1(4) C(10)-C(11)-H(11) 121.0 C(12)-C(11)-H(11) 121.0 C(13)-C(12)-C(11) 123.2(4) C(13)-C(12)-N(4) 118.5(4) C(11)-C(12)-N(4) 118.2(4) C(12)-C(13)-C(14) 118.5(4) C(12)-C(13)-H(13) 120.8 C(14)-C(13)-H(13) 120.8 C(13)-C(14)-C(9) 119.4(3) C(13)-C(14)-H(14) 120.3 C(9)-C(14)-H(14) 120.3 Symmetry transformations used to generate equivalent atoms: 4). Anisotropic displacement parameters (Å 2 x 10 3 ) for cd17083. The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U 11 +... + 2 h k a* b* U 12 ] S14

U 11 U 22 U 33 U 23 U 13 U 12 F(1) 77(2) 37(1) 58(1) 4(1) 31(1) 15(1) F(2) 85(2) 43(1) 63(2) -10(1) 27(1) -30(1) N(1) 43(2) 45(2) 40(2) -5(2) 16(1) -5(2) N(2) 43(2) 38(2) 39(2) -4(2) 13(1) -5(2) N(3) 39(2) 36(2) 45(2) -4(2) 13(1) -2(2) N(4) 81(3) 50(2) 42(2) 4(2) 23(2) 11(2) O(1) 50(2) 48(2) 55(2) -7(1) 21(1) -5(1) O(2) 103(3) 102(3) 71(2) 44(2) 30(2) 46(2) O(3) 104(3) 91(3) 83(2) 29(2) 41(2) -14(2) C(1) 50(2) 31(2) 41(2) -5(2) 16(2) -2(2) C(2) 59(3) 73(3) 68(3) -20(3) 21(2) -24(3) C(3) 83(4) 61(3) 55(3) -29(2) 12(2) -25(3) C(4) 84(3) 52(3) 50(3) -10(2) 28(2) -1(3) C(5) 55(3) 62(3) 55(3) -12(2) 22(2) -4(2) C(6) 45(2) 37(2) 35(2) 0(2) 13(2) -1(2) C(7) 48(2) 30(2) 36(2) 5(2) 10(2) -2(2) C(8) 51(2) 30(2) 45(2) 0(2) 20(2) -5(2) C(9) 43(2) 27(2) 27(2) -5(2) 7(2) -2(2) C(10) 39(2) 42(2) 46(2) 0(2) 16(2) -6(2) C(11) 47(2) 48(3) 42(2) -2(2) 9(2) 7(2) C(12) 57(3) 34(2) 30(2) -2(2) 12(2) 1(2) C(13) 48(2) 47(3) 55(2) 4(2) 20(2) -1(2) C(14) 37(2) 44(2) 47(2) 5(2) 9(2) 2(2) 5). Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for cd17083. x y z U(eq) H(2) 2702 5172 492 79 H(3) 3191 3018-91 81 H(4) 4220 3890-79 72 H(5) 4825 7044 493 67 H(10) 4581 6896 3012 49 H(11) 4639 3509 3645 55 H(13) 2755 3965 3465 59 H(14) 2695 7281 2819 51 S15

6). Torsion angles [ ] for cd17083. C(8)-N(2)-N(3)-C(9) 176.0(3) C(7)-O(1)-C(1)-C(6) 0.3(4) C(7)-O(1)-C(1)-C(2) 177.9(4) C(6)-C(1)-C(2)-C(3) -1.5(7) O(1)-C(1)-C(2)-C(3) -178.8(4) C(1)-C(2)-C(3)-C(4) 1.1(7) C(2)-C(3)-C(4)-C(5) -0.8(8) C(3)-C(4)-C(5)-C(6) 0.8(7) C(2)-C(1)-C(6)-C(5) 1.6(6) O(1)-C(1)-C(6)-C(5) 179.4(4) C(2)-C(1)-C(6)-N(1) -178.1(4) O(1)-C(1)-C(6)-N(1) -0.3(4) C(4)-C(5)-C(6)-C(1) -1.2(6) C(4)-C(5)-C(6)-N(1) 178.4(4) C(7)-N(1)-C(6)-C(1) 0.2(4) C(7)-N(1)-C(6)-C(5) -179.4(4) C(6)-N(1)-C(7)-O(1) 0.0(4) C(6)-N(1)-C(7)-C(8) 174.6(4) C(1)-O(1)-C(7)-N(1) -0.2(4) C(1)-O(1)-C(7)-C(8) -175.3(3) N(3)-N(2)-C(8)-F(1) 29.3(4) N(3)-N(2)-C(8)-F(2) 145.9(3) N(3)-N(2)-C(8)-C(7) -95.7(4) N(1)-C(7)-C(8)-F(1) 142.7(4) O(1)-C(7)-C(8)-F(1) -42.7(4) N(1)-C(7)-C(8)-F(2) 25.1(5) O(1)-C(7)-C(8)-F(2) -160.3(3) N(1)-C(7)-C(8)-N(2) -90.9(4) O(1)-C(7)-C(8)-N(2) 83.7(4) N(2)-N(3)-C(9)-C(10) -3.0(5) N(2)-N(3)-C(9)-C(14) 178.4(3) C(14)-C(9)-C(10)-C(11) 1.0(5) N(3)-C(9)-C(10)-C(11) -177.4(3) C(9)-C(10)-C(11)-C(12) -1.8(5) C(10)-C(11)-C(12)-C(13) 1.9(6) C(10)-C(11)-C(12)-N(4) 179.2(3) S16

O(2)-N(4)-C(12)-C(13) -177.3(4) O(3)-N(4)-C(12)-C(13) 2.0(5) O(2)-N(4)-C(12)-C(11) 5.2(5) O(3)-N(4)-C(12)-C(11) -175.5(4) C(11)-C(12)-C(13)-C(14) -1.1(6) N(4)-C(12)-C(13)-C(14) -178.5(3) C(12)-C(13)-C(14)-C(9) 0.3(6) C(10)-C(9)-C(14)-C(13) -0.3(6) N(3)-C(9)-C(14)-C(13) 178.3(3) Symmetry transformations used to generate equivalent atoms: 7). Hydrogen bonds for cd17083 [Å and ]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) C(5)-H(5)...O(2)#1 0.93 2.54 3.353(6) 145.5 C(2)-H(2)...O(3)#2 0.93 2.56 3.407(6) 151.6 C(5)-H(5)...O(2)#1 0.93 2.54 3.353(6) 145.5 C(2)-H(2)...O(3)#2 0.93 2.56 3.407(6) 151.6 C(5)-H(5)...O(2)#1 0.93 2.54 3.353(6) 145.5 C(2)-H(2)...O(3)#2 0.93 2.56 3.407(6) 151.6 C(5)-H(5)...O(2)#1 0.93 2.54 3.353(6) 145.5 C(2)-H(2)...O(3)#2 0.93 2.56 3.407(6) 151.6 C(2)-H(2)...O(3)#2 0.93 2.56 3.407(6) 151.6 C(5)-H(5)...O(2)#1 0.93 2.54 3.353(6) 145.5 C(2)-H(2)...O(3)#2 0.93 2.56 3.407(6) 151.6 C(5)-H(5)...O(2)#1 0.93 2.54 3.353(6) 145.5 Symmetry transformations used to generate equivalent atoms: #1 -x+1,y+1,-z+1/2 #2 -x+1/2,y+1/2,-z+1/2 S17

7. Information of ESR Preparation of the reaction sample A 10 ml round-bottom flask was charged with silver nitrate (0.02mmol), anhydrous TsOH (0.2 mmol), 4-(ethoxycarbonyl)benzenediazonium tetrafluoroborate (2c) (0.2 mmol), sodium 1,3-oxazolic difluoromethanesulfinate 1a (0.6 mmol) and DCM (2 ml) under nitrogen atmosphere. The reaction mixture was stirred 2 min. at room temperature, then the mixture of tetr-nitrosobutane (5mg) in 0.5ml DCM was injected into. Immediately after filtration, the reaction mixture was injected into the EPR sample tube. EPR spectra of the abovementioned reaction mixtures were recorded in 3-mm sample tubes at room temperature. File List Date: 10.03.2017 Time: 10:10 File Name: Spectrum send from WinEPR ACQUISITION --- picked at 10:10 Data Point Value[g-Factor] Intensity 0 2.06386 1.1320e+005 1 2.06374 1.1007e+005 2 2.06362 1.1260e+005 3 2.06350 1.2052e+005 4 2.06339 1.1942e+005 5 2.06327 1.1371e+005 6 2.06315 1.1338e+005 7 2.06303 1.1528e+005 8 2.06291 1.1490e+005 9 2.06280 1.1237e+005 10 2.06268 1.1311e+005 11 2.06256 1.1645e+005 12 2.06244 1.1353e+005 S18

13 2.06232 1.0990e+005 14 2.06221 1.0661e+005 15 2.06209 1.0066e+005 16 2.06197 9.3910e+004 17 2.06185 9.0859e+004 18 2.06174 9.0656e+004 19 2.06162 9.1419e+004 20 2.06150 9.1304e+004 21 2.06138 9.3374e+004 22 2.06126 9.2492e+004 23 2.06115 9.3105e+004 24 2.06103 9.8033e+004 25 2.06091 1.0229e+005 26 2.06079 1.0213e+005 27 2.06068 9.8357e+004 28 2.06056 9.6699e+004 29 2.06044 9.6125e+004 30 2.06032 9.4454e+004 31 2.06021 8.9539e+004 32 2.06009 8.7717e+004 33 2.05997 8.7442e+004 34 2.05985 8.7532e+004 35 2.05974 8.9169e+004 36 2.05962 9.4439e+004 37 2.05950 9.8692e+004 38 2.05938 9.9865e+004 39 2.05927 9.8663e+004 40 2.05915 9.5298e+004 41 2.05903 8.9968e+004 42 2.05891 8.4874e+004 43 2.05880 8.2887e+004 44 2.05868 8.2652e+004 45 2.05856 8.2678e+004 46 2.05844 8.5495e+004 47 2.05833 8.6135e+004 48 2.05821 8.2106e+004 49 2.05809 8.1867e+004 50 2.05798 8.1888e+004 51 2.05786 7.9679e+004 52 2.05774 7.4690e+004 53 2.05762 7.1223e+004 54 2.05751 7.5614e+004 55 2.05739 7.3577e+004 56 2.05727 6.9849e+004 S19

57 2.05715 7.0977e+004 58 2.05704 7.3145e+004 59 2.05692 7.2122e+004 60 2.05680 7.1158e+004 61 2.05669 7.0377e+004 62 2.05657 7.1799e+004 63 2.05645 7.1997e+004 64 2.05633 7.1082e+004 65 2.05622 6.9712e+004 66 2.05610 7.3026e+004 67 2.05598 7.5304e+004 68 2.05587 7.4265e+004 69 2.05575 6.9404e+004 70 2.05563 6.8683e+004 71 2.05551 6.6891e+004 72 2.05540 7.2589e+004 73 2.05528 7.9602e+004 74 2.05516 7.9055e+004 75 2.05505 8.0225e+004 76 2.05493 8.1954e+004 77 2.05481 8.1806e+004 78 2.05470 8.2168e+004 79 2.05458 8.2175e+004 80 2.05446 7.6648e+004 81 2.05434 7.1928e+004 82 2.05423 6.8086e+004 83 2.05411 7.2564e+004 84 2.05399 7.7415e+004 85 2.05388 8.1113e+004 86 2.05376 7.7439e+004 87 2.05364 7.1475e+004 88 2.05353 7.0535e+004 89 2.05341 7.2036e+004 90 2.05329 7.3268e+004 91 2.05318 7.3565e+004 92 2.05306 7.2468e+004 93 2.05294 7.5529e+004 94 2.05283 7.6947e+004 95 2.05271 8.0138e+004 96 2.05259 8.4893e+004 97 2.05248 8.0152e+004 98 2.05236 7.5128e+004 99 2.05224 6.4522e+004 100 2.05213 5.3118e+004 S20

101 2.05201 5.4658e+004 102 2.05189 5.7869e+004 103 2.05178 6.1669e+004 104 2.05166 6.3874e+004 105 2.05154 6.5695e+004 106 2.05143 5.9843e+004 107 2.05131 5.2696e+004 108 2.05119 4.8850e+004 109 2.05108 4.0888e+004 110 2.05096 3.8079e+004 111 2.05084 3.8758e+004 112 2.05073 3.9256e+004 113 2.05061 4.0974e+004 114 2.05049 4.4262e+004 115 2.05038 4.5627e+004 116 2.05026 4.6001e+004 117 2.05015 4.9867e+004 118 2.05003 5.3939e+004 119 2.04991 5.2712e+004 120 2.04980 5.3914e+004 121 2.04968 5.9374e+004 122 2.04956 6.4703e+004 123 2.04945 6.6570e+004 124 2.04933 7.1155e+004 125 2.04921 7.2608e+004 126 2.04910 6.6265e+004 127 2.04898 6.3968e+004 128 2.04887 6.4268e+004 129 2.04875 6.2930e+004 130 2.04863 5.9511e+004 131 2.04852 5.5825e+004 132 2.04840 5.0466e+004 133 2.04828 4.3220e+004 134 2.04817 4.0512e+004 135 2.04805 3.7653e+004 136 2.04794 3.5706e+004 137 2.04782 3.4350e+004 138 2.04770 3.8402e+004 139 2.04759 4.3152e+004 140 2.04747 4.3110e+004 141 2.04736 3.7891e+004 142 2.04724 3.4347e+004 143 2.04712 3.2847e+004 144 2.04701 3.1356e+004 S21

145 2.04689 3.3234e+004 146 2.04677 3.7148e+004 147 2.04666 3.5431e+004 148 2.04654 3.2795e+004 149 2.04643 3.4783e+004 150 2.04631 3.6816e+004 151 2.04619 3.9200e+004 152 2.04608 4.5346e+004 153 2.04596 4.8528e+004 154 2.04585 4.4324e+004 155 2.04573 3.7850e+004 156 2.04562 3.2845e+004 157 2.04550 3.1534e+004 158 2.04538 2.9409e+004 159 2.04527 2.8606e+004 160 2.04515 3.1537e+004 161 2.04504 3.7468e+004 162 2.04492 4.4277e+004 163 2.04480 4.8561e+004 164 2.04469 4.7615e+004 165 2.04457 4.3004e+004 166 2.04446 3.8534e+004 167 2.04434 3.5514e+004 168 2.04423 2.9527e+004 169 2.04411 2.6446e+004 170 2.04399 2.3453e+004 171 2.04388 1.8731e+004 172 2.04376 1.5206e+004 173 2.04365 1.7768e+004 174 2.04353 2.3381e+004 175 2.04342 2.6509e+004 176 2.04330 2.9470e+004 177 2.04318 3.5684e+004 178 2.04307 4.0389e+004 179 2.04295 4.1973e+004 180 2.04284 4.1879e+004 181 2.04272 3.6692e+004 182 2.04261 3.4780e+004 183 2.04249 3.2273e+004 184 2.04237 3.0981e+004 185 2.04226 2.6083e+004 186 2.04214 1.8665e+004 187 2.04203 1.5064e+004 188 2.04191 1.8260e+004 S22

189 2.04180 2.5751e+004 190 2.04168 2.9661e+004 191 2.04157 3.0428e+004 192 2.04145 3.5112e+004 193 2.04134 3.8468e+004 194 2.04122 4.3759e+004 195 2.04110 4.8590e+004 196 2.04099 4.7588e+004 197 2.04087 3.8047e+004 198 2.04076 3.1200e+004 199 2.04064 3.2132e+004 200 2.04053 2.8141e+004 201 2.04041 2.2281e+004 202 2.04030 1.6243e+004 203 2.04018 1.8090e+004 204 2.04007 1.9302e+004 205 2.03995 1.6489e+004 206 2.03984 1.5077e+004 207 2.03972 1.6903e+004 208 2.03961 2.1394e+004 209 2.03949 2.3074e+004 210 2.03938 2.1963e+004 211 2.03926 2.4672e+004 212 2.03914 2.0052e+004 213 2.03903 1.6782e+004 214 2.03891 1.5420e+004 215 2.03880 1.6893e+004 216 2.03868 1.5908e+004 217 2.03857 1.5962e+004 218 2.03845 1.7832e+004 219 2.03834 1.2469e+004 220 2.03822 1.1826e+004 221 2.03811 1.3415e+004 222 2.03799 1.0370e+004 223 2.03788 9.2436e+003 224 2.03776 1.4622e+004 225 2.03765 1.9272e+004 226 2.03753 2.1014e+004 227 2.03742 2.4429e+004 228 2.03730 2.1619e+004 229 2.03719 1.6944e+004 230 2.03707 1.5182e+004 231 2.03696 1.0409e+004 232 2.03684 1.0834e+004 S23

233 2.03673 1.7154e+004 234 2.03661 2.2194e+004 235 2.03650 2.6238e+004 236 2.03638 2.6421e+004 237 2.03627 2.3642e+004 238 2.03615 2.1241e+004 239 2.03604 2.1013e+004 240 2.03593 2.2013e+004 241 2.03581 2.3237e+004 242 2.03570 2.1369e+004 243 2.03558 1.7646e+004 244 2.03547 1.6711e+004 245 2.03535 2.1134e+004 246 2.03524 2.4450e+004 247 2.03512 2.3785e+004 248 2.03501 2.2713e+004 249 2.03489 1.9664e+004 250 2.03478 1.5032e+004 251 2.03466 1.3623e+004 252 2.03455 1.8577e+004 253 2.03443 1.8356e+004 254 2.03432 1.4280e+004 255 2.03420 1.4566e+004 256 2.03409 1.1277e+004 257 2.03398 4.2676e+003 258 2.03386 6.6896e+003 259 2.03375 1.1909e+004 260 2.03363 1.3778e+004 261 2.03352 1.2929e+004 262 2.03340 1.6599e+004 263 2.03329 1.8250e+004 264 2.03317 1.4056e+004 265 2.03306 9.4036e+003 266 2.03294 5.3886e+003 267 2.03283 2.8446e+003 268 2.03272 4.4886e+003 269 2.03260 7.1806e+003 270 2.03249 8.0546e+003 271 2.03237 6.7326e+003 272 2.03226 7.9956e+003 273 2.03214 1.1989e+004 274 2.03203 1.1803e+004 275 2.03191 1.0104e+004 276 2.03180 1.4206e+004 S24

277 2.03169 1.7585e+004 278 2.03157 1.7329e+004 279 2.03146 1.4516e+004 280 2.03134 1.0963e+004 281 2.03123 1.3100e+004 282 2.03111 9.5546e+003 283 2.03100 5.2416e+003 284 2.03089 2.5116e+003 285 2.03077 2.5316e+003 286 2.03066 4.0536e+003 287 2.03054 1.9946e+003 288 2.03043 3.7357e+002 289 2.03032-2.6432e+001 290 2.03020 2.7196e+003 291 2.03009 3.8706e+003 292 2.02997 1.7766e+003 293 2.02986 7.9757e+002 294 2.02974 6.9506e+003 295 2.02963 1.2195e+004 296 2.02952 1.8403e+004 297 2.02940 2.2287e+004 298 2.02929 1.7488e+004 299 2.02917 1.6787e+004 300 2.02906 1.7709e+004 301 2.02895 1.7408e+004 302 2.02883 1.8115e+004 303 2.02872 1.4015e+004 304 2.02860 8.6406e+003 305 2.02849 5.1816e+003 306 2.02838 5.8156e+003 307 2.02826 6.7106e+003 308 2.02815 4.0406e+003 309 2.02803 1.1776e+003 310 2.02792-3.3714e+003 311 2.02781-1.8064e+003 312 2.02769 3.6336e+003 313 2.02758 9.9966e+003 314 2.02746 1.1926e+004 315 2.02735 1.1241e+004 316 2.02724 1.1663e+004 317 2.02712 1.3417e+004 318 2.02701 1.4338e+004 319 2.02690 8.0166e+003 320 2.02678 5.8957e+002 S25

321 2.02667-4.2014e+003 322 2.02655-9.3994e+003 323 2.02644-1.5136e+004 324 2.02633-2.0411e+004 325 2.02621-1.5860e+004 326 2.02610-8.0074e+003 327 2.02599-1.3934e+003 328 2.02587 5.0326e+003 329 2.02576 1.1107e+004 330 2.02564 1.2917e+004 331 2.02553 1.3867e+004 332 2.02542 1.1225e+004 333 2.02530 6.5966e+003 334 2.02519 5.5376e+003 335 2.02508 8.8957e+002 336 2.02496-8.1334e+003 337 2.02485-1.5840e+004 338 2.02474-1.6385e+004 339 2.02462-1.0535e+004 340 2.02451-1.1094e+003 341 2.02440 6.3986e+003 342 2.02428 5.9216e+003 343 2.02417 6.5006e+003 344 2.02405 9.1916e+003 345 2.02394 6.4786e+003 346 2.02383 2.8096e+003 347 2.02371 5.6357e+002 348 2.02360-7.9643e+002 349 2.02349-5.5643e+002 350 2.02337 3.3736e+003 351 2.02326 8.1226e+003 352 2.02315 1.2083e+004 353 2.02303 1.2245e+004 354 2.02292 1.2643e+004 355 2.02281 1.4755e+004 356 2.02269 1.2523e+004 357 2.02258 8.7336e+003 358 2.02247 8.4926e+003 359 2.02235 1.6558e+004 360 2.02224 2.5908e+004 361 2.02213 3.1909e+004 362 2.02201 3.5278e+004 363 2.02190 3.4985e+004 364 2.02179 2.8330e+004 S26

365 2.02167 1.8680e+004 366 2.02156 1.2491e+004 367 2.02145 9.1856e+003 368 2.02134 7.6256e+003 369 2.02122 9.1946e+003 370 2.02111 1.8102e+004 371 2.02100 2.5475e+004 372 2.02088 2.4222e+004 373 2.02077 2.3436e+004 374 2.02066 1.9660e+004 375 2.02054 2.0749e+004 376 2.02043 2.3783e+004 377 2.02032 2.5778e+004 378 2.02020 2.5710e+004 379 2.02009 2.4096e+004 380 2.01998 2.2761e+004 381 2.01987 2.2340e+004 382 2.01975 2.2112e+004 383 2.01964 1.8785e+004 384 2.01953 1.2982e+004 385 2.01941 1.1187e+004 386 2.01930 1.4337e+004 387 2.01919 1.4090e+004 388 2.01907 1.3336e+004 389 2.01896 1.5129e+004 390 2.01885 1.8510e+004 391 2.01874 1.9018e+004 392 2.01862 1.5549e+004 393 2.01851 1.1491e+004 394 2.01840 7.0796e+003 395 2.01828 6.1646e+003 396 2.01817 8.5226e+003 397 2.01806 1.1299e+004 398 2.01795 1.4870e+004 399 2.01783 2.3162e+004 400 2.01772 2.9316e+004 401 2.01761 3.3785e+004 402 2.01749 4.1003e+004 403 2.01738 4.6738e+004 404 2.01727 5.0817e+004 405 2.01716 5.3386e+004 406 2.01704 5.2258e+004 407 2.01693 5.0345e+004 408 2.01682 4.7849e+004 S27

409 2.01671 4.6118e+004 410 2.01659 4.2254e+004 411 2.01648 4.2416e+004 412 2.01637 4.1151e+004 413 2.01626 3.7661e+004 414 2.01614 3.5665e+004 415 2.01603 3.7042e+004 416 2.01592 4.5539e+004 417 2.01581 6.6787e+004 418 2.01569 8.9393e+004 419 2.01558 1.0626e+005 420 2.01547 1.2004e+005 421 2.01535 1.2595e+005 422 2.01524 1.2811e+005 423 2.01513 1.1689e+005 424 2.01502 9.5082e+004 425 2.01491 6.5984e+004 426 2.01479 2.8469e+004 427 2.01468-1.2240e+004 428 2.01457-5.0377e+004 429 2.01446-8.0369e+004 430 2.01434-1.0008e+005 431 2.01423-1.0106e+005 432 2.01412-9.1895e+004 433 2.01401-7.7672e+004 434 2.01389-5.8161e+004 435 2.01378-4.2721e+004 436 2.01367-3.3140e+004 437 2.01356-2.2395e+004 438 2.01344-1.4430e+004 439 2.01333-8.3614e+003 440 2.01322-2.4454e+003 441 2.01311 4.4306e+003 442 2.01300 3.7606e+003 443 2.01288-5.6343e+002 444 2.01277-4.4143e+002 445 2.01266 2.1466e+003 446 2.01255 6.5496e+003 447 2.01243 1.2634e+004 448 2.01232 1.5122e+004 449 2.01221 1.6607e+004 450 2.01210 1.2868e+004 451 2.01199 1.2142e+004 452 2.01187 1.3580e+004 S28

453 2.01176 1.4487e+004 454 2.01165 1.7056e+004 455 2.01154 1.8466e+004 456 2.01143 2.1686e+004 457 2.01131 2.0291e+004 458 2.01120 1.9657e+004 459 2.01109 2.2984e+004 460 2.01098 2.9594e+004 461 2.01086 3.5607e+004 462 2.01075 3.6158e+004 463 2.01064 3.3569e+004 464 2.01053 3.1559e+004 465 2.01042 3.4315e+004 466 2.01031 4.0650e+004 467 2.01019 3.8879e+004 468 2.01008 3.6723e+004 469 2.00997 3.5811e+004 470 2.00986 3.8923e+004 471 2.00975 4.3244e+004 472 2.00963 4.9694e+004 473 2.00952 4.9576e+004 474 2.00941 4.9156e+004 475 2.00930 5.0546e+004 476 2.00919 5.1582e+004 477 2.00907 5.9000e+004 478 2.00896 7.0816e+004 479 2.00885 8.1752e+004 480 2.00874 9.6175e+004 481 2.00863 1.1324e+005 482 2.00852 1.3093e+005 483 2.00840 1.4207e+005 484 2.00829 1.4597e+005 485 2.00818 1.3921e+005 486 2.00807 1.2235e+005 487 2.00796 9.9815e+004 488 2.00785 6.8755e+004 489 2.00773 3.0608e+004 490 2.00762-4.7294e+003 491 2.00751-3.9090e+004 492 2.00740-6.8734e+004 493 2.00729-7.9658e+004 494 2.00718-7.7702e+004 495 2.00706-6.3305e+004 496 2.00695-4.4337e+004 S29

497 2.00684-3.1617e+004 498 2.00673-2.3573e+004 499 2.00662-1.5941e+004 500 2.00651-1.1249e+004 501 2.00639-7.4814e+003 502 2.00628-8.3044e+003 503 2.00617-6.3734e+003 504 2.00606-4.1804e+003 505 2.00595-4.1194e+003 506 2.00584-7.6124e+003 507 2.00573-8.1094e+003 508 2.00561-5.1754e+003 509 2.00550-6.2634e+003 510 2.00539-7.5424e+003 511 2.00528-1.0376e+004 512 2.00517-1.1423e+004 513 2.00506-8.9894e+003 514 2.00495-7.7174e+003 515 2.00484-8.3674e+003 516 2.00472-7.6864e+003 517 2.00461-7.5484e+003 518 2.00450-9.3614e+003 519 2.00439-1.4619e+004 520 2.00428-2.1103e+004 521 2.00417-2.6026e+004 522 2.00406-3.5230e+004 523 2.00394-4.1499e+004 524 2.00383-4.5412e+004 525 2.00372-4.6149e+004 526 2.00361-4.7891e+004 527 2.00350-5.1511e+004 528 2.00339-5.3647e+004 529 2.00328-5.5377e+004 530 2.00317-6.0157e+004 531 2.00306-6.9234e+004 532 2.00294-8.0740e+004 533 2.00283-8.8064e+004 534 2.00272-8.6363e+004 535 2.00261-7.4497e+004 536 2.00250-5.5275e+004 537 2.00239-3.0200e+004 538 2.00228-1.1525e+004 539 2.00217-2.5724e+003 540 2.00206 9.7926e+003 S30

541 2.00194 2.5457e+004 542 2.00183 4.2755e+004 543 2.00172 5.9149e+004 544 2.00161 7.6022e+004 545 2.00150 9.1504e+004 546 2.00139 9.6242e+004 547 2.00128 8.9988e+004 548 2.00117 7.5288e+004 549 2.00106 5.2079e+004 550 2.00095 2.0412e+004 551 2.00084-1.3572e+004 552 2.00072-4.7786e+004 553 2.00061-7.6192e+004 554 2.00050-9.8061e+004 555 2.00039-1.1675e+005 556 2.00028-1.2032e+005 557 2.00017-1.1631e+005 558 2.00006-1.0315e+005 559 1.99995-8.8080e+004 560 1.99984-7.5529e+004 561 1.99973-6.0916e+004 562 1.99962-4.9265e+004 563 1.99951-4.2234e+004 564 1.99939-4.0888e+004 565 1.99928-4.3794e+004 566 1.99917-4.7187e+004 567 1.99906-5.0510e+004 568 1.99895-5.0729e+004 569 1.99884-4.6798e+004 570 1.99873-3.8403e+004 571 1.99862-3.3013e+004 572 1.99851-3.0898e+004 573 1.99840-3.1613e+004 574 1.99829-3.0336e+004 575 1.99818-2.6628e+004 576 1.99807-2.4204e+004 577 1.99796-2.2309e+004 578 1.99785-2.1635e+004 579 1.99774-2.1807e+004 580 1.99762-2.0371e+004 581 1.99751-2.0488e+004 582 1.99740-2.2082e+004 583 1.99729-2.2267e+004 584 1.99718-2.3491e+004 S31

585 1.99707-2.7707e+004 586 1.99696-3.1369e+004 587 1.99685-3.0601e+004 588 1.99674-3.3876e+004 589 1.99663-4.1003e+004 590 1.99652-4.7645e+004 591 1.99641-4.7725e+004 592 1.99630-4.8884e+004 593 1.99619-4.9732e+004 594 1.99608-4.7808e+004 595 1.99597-4.7872e+004 596 1.99586-5.0166e+004 597 1.99575-5.1871e+004 598 1.99564-4.9159e+004 599 1.99553-5.1224e+004 600 1.99542-5.1511e+004 601 1.99531-5.3927e+004 602 1.99520-5.2979e+004 603 1.99509-5.1844e+004 604 1.99498-4.9757e+004 605 1.99487-5.1453e+004 606 1.99476-5.2913e+004 607 1.99465-5.1255e+004 608 1.99453-4.9046e+004 609 1.99442-4.8155e+004 610 1.99431-4.6797e+004 611 1.99420-4.1124e+004 612 1.99409-3.6070e+004 613 1.99398-3.3666e+004 614 1.99387-3.3119e+004 615 1.99376-3.2247e+004 616 1.99365-3.1645e+004 617 1.99354-3.6057e+004 618 1.99343-4.2271e+004 619 1.99332-4.4850e+004 620 1.99321-4.8031e+004 621 1.99310-4.7393e+004 622 1.99299-4.3258e+004 623 1.99288-4.1823e+004 624 1.99277-3.8083e+004 625 1.99266-3.7696e+004 626 1.99255-4.0757e+004 627 1.99244-3.6133e+004 628 1.99233-3.6864e+004 S32

629 1.99222-4.2119e+004 630 1.99211-4.3885e+004 631 1.99200-4.6565e+004 632 1.99189-4.3707e+004 633 1.99178-3.8324e+004 634 1.99167-3.4846e+004 635 1.99156-3.6253e+004 636 1.99145-3.5777e+004 637 1.99134-3.1909e+004 638 1.99123-3.0621e+004 639 1.99112-3.0270e+004 640 1.99102-2.9095e+004 641 1.99091-3.2529e+004 642 1.99080-3.7045e+004 643 1.99069-3.9655e+004 644 1.99058-3.9687e+004 645 1.99047-3.8090e+004 646 1.99036-3.6390e+004 647 1.99025-3.3200e+004 648 1.99014-2.9339e+004 649 1.99003-2.9351e+004 650 1.98992-3.0174e+004 651 1.98981-3.6272e+004 652 1.98970-3.8454e+004 653 1.98959-4.2007e+004 654 1.98948-4.2170e+004 655 1.98937-4.3265e+004 656 1.98926-4.6462e+004 657 1.98915-4.8971e+004 658 1.98904-5.0195e+004 659 1.98893-4.8734e+004 660 1.98882-4.5409e+004 661 1.98871-3.9994e+004 662 1.98860-3.7460e+004 663 1.98849-3.4254e+004 664 1.98838-3.0812e+004 665 1.98827-3.0655e+004 666 1.98816-3.1437e+004 667 1.98805-2.8362e+004 668 1.98795-2.9540e+004 669 1.98784-3.1857e+004 670 1.98773-3.2671e+004 671 1.98762-2.6880e+004 672 1.98751-1.9122e+004 S33

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