Ag-Initiated gem-difluoromethylenation of the Nitrogen Center of. Arenediazonium Salts to gem-difluoromethylene Azo Compounds
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1 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, , P. R. China Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, , P. R. China Laboratory for Microstructures, Shanghai University, Shanghai, , 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 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 - S H NMR, 13 C NMR and 19 F NMR Spectrums for all Compounds S42 - S87 S1
2 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 ( 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: (m, 2H), (m, 2H); 19 F NMR (470 MHz, DMSO-d 6 ) δ ; 13 C NMR (125 MHz, DMSO-d 6 ) δ: (t, 2 J C-F = 30.3 Hz), 150.9, 140.6, 126.6, 125.5, (t, 1 J C-F = 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 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 ; 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
3 126.5 (t, 1 J C-F = 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 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 ; 13 C NMR (125 MHz, DMSO-d 6 ) δ (t, J = 27.4 Hz), 152.4, 135.1, 126.5, (t, J = Hz), 125.8, 123.5, 122.3; (KBr, cm -1 ) v: 3065, 1635,1557,1509, 1458, 1248, 1029, 759, 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) mg, 81% yield, light yellow solid, Mp 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), (m, 1H), (m, 2H), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: , (m); 13 C NMR (125 MHz, CDCl 3 ) δ:161.8 (d, 1 J C-F = Hz), (t, 2 J C-F = 37.8 Hz), 150.9, 139.9, (d, 3 J C-F = 6.5 Hz), (d, 3 J C-F = 8.8 Hz), 127.1, 125.5, 124.5, 121.5, 118.3, (d, 2 J C-F = 19.3 Hz), (t, 1 J C-F = 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: , found: Ethyl 2-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzoate (3ab) mg, 96% yield, light yellow solid, Mp 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), (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: ; 13 C NMR (125 MHz, CDCl 3 ) δ: 166.1, (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, (t, 1 J C-F = 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 : , found: S3
4 Ethyl 4-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzoate (3ac) mg, 95% yield, light brown solid, Mp 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), (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: ; 13 C NMR (125 MHz, CDCl 3 ) δ: 165.3, (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, (t, 1 J C-F = 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 : , found: Ethyl 3-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzoate (3ad) mg, 70% yield, light brown solid, Mp 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), (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 C NMR (125 MHz, CDCl 3 ) δ 165.3, (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, (t, 1 J C-F = Hz), 111.5, 61.6, 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 : , found: (4-((Benzo[d]oxazol-2-yldifluoromethyl)diazenyl)phenyl)ethan-1-one (3ae) mg, 76% yield, light yellow solid, Mp 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), (m, 2H), 2.62 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: 197.0, (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, (t, 1 J C-F = 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 : , found: (2-((Benzo[d]oxazol-2-yldifluoromethyl)diazenyl)phenyl)(phenyl)methanone (3af) mg, 93% yield, yellow solid, Mp o C; 1 H NMR (500 MHz, CDCl 3 ) δ: (m, 1H), (m, 3H), (m, 1H), (m, 5H), (m, 1H), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ 195.3, (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, (t, 1 J C-F = 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 : , found: ((Benzo[d]oxazol-2-yldifluoromethyl)diazenyl)benzonitrile (3ag) S4
5 101.3 mg, 68% yield, light yellow solid, Mp 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), (m, 2H); 19 F NMR (471 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (Difluoro((4-nitrophenyl)diazenyl)methyl)benzo[d]oxazole (3ah) 87.5 mg, 55% yield, yellow solid, Mp 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), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (t, 2 J C-F = 37.6 Hz), 153.1, 150.9, 150.6, 139.9, 127.3, 125.7, 124.8, 121.6, (t, 1 J C-F = 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 : , found: (Difluoro((4-(trifluoromethyl)phenyl)diazenyl)methyl)benzo[d]oxazole (3ai) 93.8 mg, 55% yield, brown solid, Mp 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), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: , ; 13 C NMR (125 MHz, CDCl 3 ) δ: (t, 2 J C-F = 37.8 Hz), 151.5, 150.4, 139.4, (q, 2 J C-F = 33.0 Hz), 126.7, (q, 3 J C-F = 3.7 Hz), 125.1, 124.0, (q, 1 J C-F = Hz) 121.1, (t, 1 J C-F = 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: , found: (Difluoro((2-fluorophenyl)diazenyl)methyl)benzo[d]oxazole (3aj) 75.7 mg, 52% yield, light yellow solid, Mp 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), (m, 2H), 7.18 (t, J = 8.5 Hz, 2H). 19 F NMR (470 MHz, CDCl 3 ) δ , (m). 13 C NMR (125 MHz, CDCl 3 ) δ (d, 1 J C-F = Hz), (t, 2 J C-F = 38.3 Hz), 150.9, , 139.9, 127.0, 126.7, 126.7, 125.5, 121.5, (t, 1 J C-F = Hz), (d, 2 J C-F = 23.2 Hz), 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: , found: (((2,4-Difluorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3ak) mg, 74% yield, yellow solid, Mp o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.82 (d, J = 7.9 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: , , ; 13 C NMR (125 MHz, CDCl 3 ) δ: (t, 2 J C-F = 38.1 Hz), (dd, 1 J C-F = 245.0, 3 J C-F = 13.7 Hz), (dd, 1 J C-F = Hz, 3 J C-F = 13.7 Hz), 151.7, (t, J = 4.1 Hz), 139.9, 127.1, 125.5, (dd, J = 2.5, 7.0 Hz), 121.4, (d, 2 J C-F = 18.7 Hz), (t, S5
6 1 J C-F = Hz), 111.4, (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: , found: (((4-Chlorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3al) mg, 76% yield, yellow solid, Mp 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), (m, 4H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (((2-Chlorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3am) mg, 66% yield, pale yellow solid, Mp o C; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.81 (d, J = 7.2 Hz, 1H), (m, 1H), (m,1h), (m, 4H), (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (((4-Bromophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3an) mg, 73% yield, brown solid, Mp 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), (m, 3H), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 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, (t, 1 J C-F = Hz), 111.5; IR (KBr, cm -1 ): v: 3090, , 1400, 1301, 1183, 1107, 840, 748; HRMS (EI TOF) calcd for (M+) C 14 H 8 BrF 2 N 3 O: , found: (((2-Bromophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3ao) mg, 74% yield, light yellow solid, Mp o C; 1 H NMR (500 MHz, CDCl 3 ) δ: (m, 1H), (m, 2H), 7.60 (d, J = 7.8 Hz, 1H), (m, 4H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 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, (t, 1 J C-F = 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: , found: (Difluoro((4-iodophenyl)diazenyl)methyl)benzo[d]oxazole (3ap) mg, 55% yield, yellow solid, Mp o C; 1 H NMR (500 MHz,CDCl 3 ) δ: (m, 3H), (m, 3H), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, S6
7 CDCl 3 ) δ: (t, 2 J C-F = 38.1 Hz), 150.9, 149.6, 139.9, 138.8, 127.1, 125.5, 125.5, 121.5, (t, 1 J C-F = 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: , found: (Difluoro((2-iodophenyl)diazenyl)methyl)benzo[d]oxazole (3aq) 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), (m, 1H), (m, 2H), (m, 3H), (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (((4-Bromo-2-chlorophenyl)diazenyl)difluoromethyl)benzo[d]oxazole (3ar) mg, 79% yield, light yellow solid, Mp 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), (m, 2H), (m, 2H), 7.40 (td, J = 7.7, 1.2 Hz, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (Difluoro((4'-fluoro-[1,1'-biphenyl]-4-yl)diazenyl)methyl)benzo[d]oxazole (3as) mg, 69% yield, light yellow solid, Mp 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), (m, 2H), (m, 2H), 7.15 (t, J = 8.6 Hz, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: , (m); 13 C NMR (125 MHz, CDCl 3 ) δ: (d, 1 J = Hz), (t, 2 J C-F = 38.6 Hz), 150.4, 148.9, 145.5, 139.5, 135.0, (d, 3 J = 8.3 Hz), 127.3, 126.9, 125.2, 124.4, 121.3, (t, 1 J C-F = Hz), (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: , found: (Difluoro(phenyldiazenyl)methyl)benzo[d]oxazole (3at) 61.4 mg, 45% yield, light brown solid, Mp o C; 1 H NMR (500 MHz, CDCl 3 ) δ: (m, 3H), (m, 1H), (m, 1H), (m, 3H), (m, 1H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (Difluoro(p-tolyldiazenyl)methyl)benzo[d]oxazole (3au) S7
8 109.1 mg, 76% yield, brown solid, Mp 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), (m, 2H), 7.19 (d, J = 8.1 Hz, 2H), 2.33 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (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, (t, 1 J C-F = 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: , found: (Difluoro((4-methoxyphenyl)diazenyl)methyl)benzo[d]oxazole (3av) 57.6 mg, 38% yield, brown solid, Mp o C; 1 H NMR (500 MHz, CDCl 3 ) δ: (m, 3H), 7.60 (d, J = 8.0 Hz, 1H), (m, 2H), 6.94 (d, J = 8.0 Hz, 2H), 3.83 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: 164.7, (t, 2 J C-F = 38.8 Hz), 150.9, 144.7, 140.0, 126.9, 126.7, 125.3, 121.5, (t, 1 J C-F = 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 : , found: (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: ; 13 C NMR (125 MHz, CDCl 3 ) δ: 154.4, (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, (t, 1 J C-F = 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: , found: Methyl-3-((benzo[d]oxazol-2-yldifluoromethyl)diazenyl)thiophene-2-carboxylate (3ax) mg, 85% yield, brown solid, Mp 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), (m, 4H), 3.34 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ:161.2, (t, 2 J C-F = 37.8 Hz), 152.0, 151.0, 140.0, 138.0, 130.5, 126.9, 125.4, 121.5, (t, 1 J C-F = 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: , found: (Difluoro((1-methyl-4,5-dihydro-1H-pyrazol-3-yl)diazenyl)methyl)benzo[d]oxazole (3ay) 65.7 mg, 66 % yield, brown solid, Mp 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), (m, 3H), 6.70 (d, J = 2.5 Hz, 1H), 3.99 (s, 3H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: 161.4, (t, 2 J C-F = 38.5 Hz), 150.9, 139.9, S8
9 132.6, 126.9, 125.3, 121.4, (t, 1 J C-F = 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: , found: Ethyl 4-((difluoro(5-methylbenzo[d]oxazol-2-yl)methyl)diazenyl)benzoate (3bc) 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 ; 13 C NMR (125 MHz, CDCl 3 ) δ 165.4, (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, (t, 1 J C-F = 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 : , found: (E)-2-(((4-Chlorophenyl)diazenyl)difluoromethyl)benzo[d]thiazole (3cl) mg, 74%, Yellow solid, mp: ; 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 ; 13 C NMR (125 MHz, CDCl 3 ) δ (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, (t, 1 J C-F = 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: , found: 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, 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) mg, 57% yield, yellow solid, Mp 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), (m, 2H); 19 F NMR (470 MHz, CDCl 3 ) δ: ; 13 C NMR (125 MHz, CDCl 3 ) δ: (t, 2 J C-F = 37.6 Hz), 153.1, 150.9, 150.6, 139.9, 127.3, 125.7, 124.8, 121.6, (t, 1 J C-F = Hz), 111.5; IR (KBr, cm -1 ): v: 3069, 1607, 1528, 1116, 1044, 807, 754 S9
10 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) CuI (0.5) THF 6.0 TsOH (1.0) CuI (0.5) DMSO 6.0 TsOH (1.0) 0 21 CuI (0.5) Dioxane 6.0 TsOH (1.0) 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 TsOH(1.0) 69 3 AgNO 3 (0.5) CH 2 Cl TsOH(1.0) AlCl 3 (0.5) CH 2 Cl TsOH(1.0) ZnCl 2 (0.5) CH 2 Cl TsOH(1.0) CuSCN (0.5) CH 2 Cl TsOH(1.0) CuSO 4 (0.5) CH 2 Cl TsOH(1.0) 68 4 AgOAc (0.5) CH 2 Cl TsOH(1.0) AgNO 3 (0.5) CH 2 Cl HCl(1.0) AgNO 3 (0.5) CH 2 Cl CH 3 COOH(1.0) AgNO 3 (0.5) CH 2 Cl TFA(1.0) AgNO 3 (0.5) CH 2 Cl PhCOOH(1.0) AgNO 3 (0.1) CH 2 Cl TsOH (0.1) AgNO 3 (0.1) CH 2 Cl TsOH(0.5) AgNO 3 (0.1) CH 2 Cl TsOH(0.5) 70 5 AgNO 3 (0.5) CH 2 Cl TsOH(1.0) 85 6 AgNO 3 (0.5) CH 2 Cl / 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) AgNO 3 (0.2) CH 2 Cl 2 / TsOH (0.5) AgNO 3 (0.1) CH 2 Cl 2 / / / CH 2 Cl 2 / / / CH 2 Cl TsOH(1.0) / CH 2 Cl TsOH(0.5) / CH 2 Cl / / CH 2 Cl / b AgNO 3 (0.1) CH 2 Cl 2 / TsOH (1.0) c AgNO 3 (0.1) CH 2 Cl 2 / TsOH (1.0) FeCl 3 (0.1) CH 2 Cl 2 / TsOH (1.0) 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
11 6. Crystal Information for 3ah (CCDC: ) 1) Crystal data and structure refinement for cd17083 Identification code cd17083 Empirical formula C14 H8 F2 N4 O3 Formula weight Temperature 293(2) K Wavelength Å Crystal system Monoclinic Space group C 2/c Unit cell dimensions a = (5) Å = 90. b = (11) Å = (6). c = (6) Å = 90. Volume (11) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1296 Crystal size x x mm 3 Theta range for data collection to Index ranges -23<=h<=25, -5<=k<=5, -32<=l<=28 Reflections collected 6851 Independent reflections 2340 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2340 / 0 / 208 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 2) Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for cd U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) S11
12 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 cd 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
13 C(1)-C(2) 1.367(5) C(2)-C(3) 1.379(6) C(2)-H(2) C(3)-C(4) 1.364(6) C(3)-H(3) C(4)-C(5) 1.366(6) C(4)-H(4) C(5)-C(6) 1.375(5) C(5)-H(5) 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) C(11)-C(12) 1.374(5) C(11)-H(11) C(12)-C(13) 1.362(5) C(13)-C(14) 1.371(5) C(13)-H(13) C(14)-H(14) 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) C(3)-C(2)-H(2) C(4)-C(3)-C(2) 122.0(4) C(4)-C(3)-H(3) C(2)-C(3)-H(3) C(3)-C(4)-C(5) 122.4(4) S13
14 C(3)-C(4)-H(4) C(5)-C(4)-H(4) C(4)-C(5)-C(6) 116.1(4) C(4)-C(5)-H(5) C(6)-C(5)-H(5) 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) C(9)-C(10)-H(10) C(10)-C(11)-C(12) 118.1(4) C(10)-C(11)-H(11) C(12)-C(11)-H(11) 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) C(14)-C(13)-H(13) C(13)-C(14)-C(9) 119.4(3) C(13)-C(14)-H(14) C(9)-C(14)-H(14) Symmetry transformations used to generate equivalent atoms: 4). Anisotropic displacement parameters (Å 2 x 10 3 ) for cd The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] S14
15 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 cd x y z U(eq) H(2) H(3) H(4) H(5) H(10) H(11) H(13) H(14) S15
16 6). Torsion angles [ ] for cd 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) (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) (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) (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) (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) (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) (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
17 O(2)-N(4)-C(12)-C(13) (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) (4) C(11)-C(12)-C(13)-C(14) -1.1(6) N(4)-C(12)-C(13)-C(14) (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)# (6) C(2)-H(2)...O(3)# (6) C(5)-H(5)...O(2)# (6) C(2)-H(2)...O(3)# (6) C(5)-H(5)...O(2)# (6) C(2)-H(2)...O(3)# (6) C(5)-H(5)...O(2)# (6) C(2)-H(2)...O(3)# (6) C(2)-H(2)...O(3)# (6) C(5)-H(5)...O(2)# (6) C(2)-H(2)...O(3)# (6) C(5)-H(5)...O(2)# (6) 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
18 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: Time: 10:10 File Name: Spectrum send from WinEPR ACQUISITION --- picked at 10:10 Data Point Value[g-Factor] Intensity e e e e e e e e e e e e e+005 S18
19 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S19
20 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S20
21 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S21
22 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S22
23 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S23
24 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S24
25 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+002 S25
26 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S26
27 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S27
28 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S28
29 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S29
30 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+003 S30
31 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S31
32 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S32
33 e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e e+004 S33
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