Copper-mediated radical cross-coupling reaction of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) with phenols or thiophenols. Support Information

Copper-mediated radical cross-coupling reaction of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) with phenols or thiophenols Dr. Xiao un Tang and Prof. Qing un Chen* Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, 200032, Shanghai, P.R. China Support Information Table of Contents 1, General Information S2 2, Experimental Procedure and Characterization S3 3, 19 F, 1 H and 13 C NMR spectra for new compounds S18 4, Reference S69 S1

1, General Information All reactions were carried out under the N 2 atmosphere,dmf and DMSO were distilled prior to use. Reagents were purchased at the commercial quality and used without further purification. 1 HNMR spectra were recorded at the Bruker 400MHz or Varian 300MHz spectrometer. Chemical shifts are reported in ppm relative to TMS as a reference (CD 3 = 7.26 ppm).the following abbreviations are used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad. 19 FNMR spectra were recorded at the Bruker 300 MHz or Varian 300 MHz spectrometer without proton decoupling. Chemical shifts are reported in ppm relative to CF 3. 13 CNMR spectra were recorded on a Bruker 100 MHz spectrometer with complete proton decoupling. Chemical shifts are reported in ppm relative to TMS as a reference (CD 3 = 77.0 ppm). IR spectra were collected on a Nicolet IN10 FT-IR spectrometer, are reported in terms of frequency of absorption (cm -1 ). EI-MS spectra were recorded on an Aligent 5973N MSD. EI-HRMS spectra were recorded on a Waters Micromass GCT Premie. ESI-MS spectra were recorded on an Aligent LC/MSD SL. ESI-HRMS spectra were recorded on an APEXIII 7.0 TESLA FTMS. S2

2, Experimental Procedure and Characterization 1) General procedure for Copper-mediated radical cross-coupling between HCFC-123 and phenols. R Cu/Et 3 N/Et 2 NH R OH HCFC-123 OCHCF 3 1 60 o C 2 A 20 ml sealed tube was charged with Cu powder (10 mmol, 0.64 g) and filled with N 2. HCFC-123 (10 ml), p-meophoh (1a, 5 mmol, 0.620 g), Et 3 N(6.25 mmol, 627 mg) and Et 2 NH (10 mmol, 0.731 g) were added into this sealed tube. The solution in the sealed tube was stirred at 60 o C for 3 h. After the solution was cool, the mixture was poured into Et 2 O (50 ml). The precipitation was removed with filtration. The solvent was removed and the residue was purified by flash chromatography on a silica gel column using PE:DCM = 5:1 as the eluent. 2a was obtained as the colorless oil (1.14 g, 95% yield). 1-(1-chloro-2,2,2-trifluoroethoxy)-4-methoxybenzene (2a) Colorless oil 19 FNMR (282 MHz, CD 3 ):-80.0(d,J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):7.06(d, J = 9 Hz,2H), 6.90(d, J = 9 Hz,2H), 6.02(q, J = 4 Hz,1H), 3.80(s, 3H); 13 CNMR (100 MHz, CD 3 ):156.8, 148.6, 120.2(q, J = 280 Hz), 118.6, 114.9, 86.9(q, J = 39Hz, 55.5z); MS (EI):240(M +, 15.71), 123(100), 95(20.29), 240(15.71), 77(11.73), 92(10.33); HRMS (EI) M + calcd for C 9 H 8 F 3 O 2 :240.0165, found 240.0164; IR (KBr) ν/cm -1 : 2958, 1749, 1507, 1383, 1289, 1249, 1208, 1147, 1094, 1034. S3

N-(4-(1-chloro-2,2,2-trifluoroethoxy)phenyl)acetamide (2b) White solid m.p.:102.7-103.5 19 FNMR (282 MHz, DMSO):-80.0(d, J = 4 Hz); 1 HNMR (400 MHz, DMSO):9.96(s,1H), 7.58(d,J = 9 Hz,2H), 7.29(q, J = 4 Hz,1H), 7.13(d,J = 9 Hz, 2H), 2.00(s,3H); 13 CNMR (100 MHz,DMSO):168.6, 149.3, 136.5, 124.0, 120.8, 120.7(q, = 280 Hz), 85.7(q, J = 38 Hz), 24.3. MS (ESI):268(M+1) + ; HRMS (ESI) (M+Na) + calcd for C 10 H 9 F 3 NO 2 :290.0166, found 290.0165; IR (KBr) ν/cm -1 :3295, 3134, 3050, 1666, 1604, 1537, 1513, 1407, 1376, 1214, 1146, 1085. (1-chloro-2,2,2-trifluoroethoxy)benzene (2c) O CF 3 Colorless oil 19 FNMR (282 MHz, CD 3 ):-80.8(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):7.37-7.40(m,2H), 7.19(t, J = 8 Hz,1H), 7.12(d, J= 8 Hz, 2H), 6.12(q, J = 4 Hz, 1H); 13 CNMR (100 MHz, CD 3 ):154.6, 129.9, 124.7, 120.2(q, J = 279 Hz), 116.6, 85.4(q, J = 40 Hz); MS (EI):210(M +, 74.72), 77(100), 65(74.37), 175(59.61), 93(59.27), 141(31.26); HRMS (EI) M + calcd for C 8 H 6 F 3 O:210.0059, found 210.0060 IR (KBr) ν/cm -1 : 3074, 2960, 1749, 1595, 1493, 1382, 1289, 1265, 1215, 1149, 1098. 2-(1-chloro-2,2,2-trifluoroethoxy)-1,4-dimethylbenzene (2d) S4

Colorless oil 19 FNMR (282 MHz, CD 3 ): -80.3(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):7.09(d,J = 8 Hz,1H),6.89-6.92(m, 2H), 6.11(q,J = 4 Hz, 1H), 2.36(s, 3H), 2.24(s, 3H); 13 CNMR (100 MHz, CD 3 ):153.0, 137.2, 131.3, 125.5, 125.2, 120.9(q, J = 279 Hz), 115.4, 86.0(q, J = 40 Hz), 21.1, 15.3; MS (EI):238(M +, 47.17), 121(100), 77(49.90), 91(41.25), 105(30.24), 203(17.06); HRMS (EI) (M-H) + calcd for C 10 H 10 F 3 O:238.0372, found 238.0373; IR (KBr) ν/cm -1 :2929, 1749, 1623, 1511, 1308, 1265, 1246, 1194, 1145, 1089. 1-(1-chloro-2,2,2-trifluoroethoxy)naphthalene (2e) White solid m.p.:46.1-47.0 19 FNMR (282 MHz, CD 3 ):-79.9(d, J = 4Hz); 1 HNMR (400 MHz, CD 3 ):8.17-8.19(m,1H), 7.84-7.86(m,1H), 7.66(d, J = 8 Hz,1H), 7.54-7.56(m, 2H), 7.41-7.45(m, 1H), 7.18(d, J = 8 Hz,1H), 6.31(q, J = 4 Hz,1H); 13 CNMR (100 MHz, CD 3 ):150.5, 149.1, 134.6, 127.6, 127.0, 125.6, 125.1, 124.5, 121.3, 120.5(q, J = 280 Hz), 109.3, 85.5(q, J = 39 Hz); MS (EI):260(M +, 26.23), 115(100), 145(87.05), 127(32.09), 126(12.55), 116(10.75); HRMS (EI) M + calcd for C 12 H 8 F 3 O:260.0216, found 260.0215; IR (KBr) ν/cm -1 : 3072, 2955, 1635, 1599, 1577, 1508, 1464, 1294, 1261, 1236, 1193, 1153, 1125. 2-(1-chloro-2,2,2-trifluoroethoxy)-1-isopropyl-4-methylbenzene (2f) S5

White solid m.p.:32.9-33.6 19 FNMR (282 MHz, CD 3 ): -80.0(d, J = 4 Hz); 1 HNMR(400 MHz, CD 3 ):7.18(d,J = 8 Hz,1H), 6.96(d, J = 8 Hz,1H), 6.68(s,1H), 6.16(q, J = 4 Hz,1H), 3.24-3.21(m,1H), 2.36(s,3H), 1.19-1.23(m,6H). 13 CNMR (100 MHz, CD 3 ):151.7, 136.9, 135.8, 126.9, 125.3, 120.9(q, J = 279Hz), 85.5(q, J = 40 Hz), 26.4, 22.8, 21.1. MS (EI):266(M +, 30.41), 251(100), 134(56.51), 91(48.26), 115(41.31),117(39.33); HRMS (EI) M + calcd for C 12 H F 3 O:266.0685, found 266.0687; IR (KBr) ν/cm -1 :2969, 1892, 1617, 1578, 1508, 1389, 1296, 1281, 1264, 1242, 1191, 1157. 1-(1-chloro-2,2,2-trifluoroethoxy)-3-nitrobenzene (2g) O 2 N O CF 3 Yellow solid m.p.:32.8-33.3 19 FNMR (282 MHz, CD 3 ): -80.0(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):8.05(d, J = 8 Hz,1H), 7.97(s, 1H), 7.58(t,J=8 Hz,1H), 7.44-7.46(m,1H), 6.19(q, J = 4 Hz,1H); 13 CNMR (100 MHz, CD 3 ):154.6, 149.1, 130.8, 121.8, 120.8(q, J = 280 Hz), 119.5, 111.7, 84.5(q, J=40 Hz); MS (EI):255(M +, 59.70), 92(100), 76(42.01), 64(40.64), 63(35.18),50(28.29); HRMS (EI) M + calcd for C 8 H 5 F 3 O 3 N:254.9910, found 254.9908; S6

IR (KBr) ν/cm -1 : 3089, 2980, 1533, 1478, 1354, 1228, 1197, 1152, 1111, 1085. 4-(1-chloro-2,2,2-trifluoroethoxy)benzonitrile (2h) Light yellow oil 19 FNMR (282 MHz, CD 3 ):-80.2(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):7.68(d,J = 9 Hz,2H),7.19(d, J = 9 Hz, 2H), 6.18(q,J = 4 Hz, 1H); 13 CNMR (100 MHz, CD 3 ):157.1, 134.3, 120.5(q,J = 280 Hz), 118.0, 117.2, 108.4, 83.7(q,J = 40 Hz); MS (EI):235(M +, 100), 102(78.80), 90(65.30), 200(59.52), 166(58.19); HRMS (EI) (M-H) + calcd for C 9 H 5 F 3 ON:235.0012, found 235.0009; IR (KBr) ν/cm -1 :2231, 1606, 1507, 1385, 1288, 1231, 1153, 1088. 4-(1-chloro-2,2,2-trifluoroethoxy)benzaldehyde (2i) Light yellow oil 19 FNMR (282 MHz, CD 3 ):-80.1(d,J=4 Hz); 1 HNMR (400 MHz, CD 3 ):9.94(s,1H),7.91(d, J = 8 Hz,2H), 7.23(d, J = 8 Hz,2H), 6.22(q, J = 4 Hz, 1H); 13 CNMR (100 MHz, CD 3 ):190.4, 158.6, 132.9, 131.9, 120.5(q, J = 280 Hz), 116.7, 83.9(q, J = 40 Hz); MS (EI):238(M +, 67.60), 237(100), 239(38.94), 65(25.56), 105(25.09), 77(23.09); HRMS (EI) (M-H) + calcd for C 9 H 5 F 3 O 2 :236.9930, found 236.9934; IR (KBr) ν/cm -1 :3077, 2835, 2744, 1698, 1602, 1589, 1507, 1387, 1225, 1153, 1089. methyl 4-(1-chloro-2,2,2-trifluoroethoxy)benzoate (2j) S7

White solid m.p.:51.2-52.2 19 FNMR (282 MHz, CD 3 ):-80.1(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):8.05(d, J = 8 Hz,2H), 7.12(d,J = 8 Hz,2H), 6.18(q,J = 4 Hz,1H), 3.88(s,3H); 13 CNMR (100 MHz, CD 3 ):166.0, 157.6, 131.8, 126.5, 120.6(q, J = 280 Hz), 116.4, 84.1(q, J = 39 Hz), 52.1; MS (EI):268(M +, 30.77), 237(100), 239(32.31), 92(30.13), 121(19.16),76(18.43); HRMS (EI) M + calcd for C 10 H 8 F 3 O 3 :268.0114, found 268.0117; IR (KBr) ν/cm -1 :2983, 1707, 1608, 1509, 1292, 1227, 1151, 1091. 3-(1-chloro-2,2,2-trifluoroethoxy)pyridine (2k) Colorless oil 19 FNMR (282 MHz, CD 3 ):-79.9(d, J = 4Hz); 1 HNMR (400 MHz, CD 3 ):8.44-8.99(d,J = 8 Hz,2H), 7.32-7.44(m,2H), 6.14(q,J = 4 Hz,1H); 13 CNMR (100 MHz, CD 3 ):151.1, 146.0, 139.6, 124.2, 124.1, 120.5(q, J = 280 Hz), 85.3(q, J = 40 Hz); MS (EI):211(M +, 14.55), 142(100), 211(71.48), 78(62.94), 91(58.15),66(56.64); HRMS (EI) M + calcd for C 7 H 5 F 3 NO:211.0012, found 211.0009; IR (KBr) ν/cm -1 :3066, 2953, 1732, 1578, 1477, 1432, 1292, 1257, 1190. 1153.. 1-chloro-4-(1-chloro-2,2,2-trifluoroethoxy)benzene (2l) S8

O CF 3 Colorless oil 19 FNMR (282 MHz, CD 3 ):-80.9(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):7.34(d, J = 9 Hz,2H), 7.05(d, J = 9 Hz,2H), 6.05(q, J=4 Hz,1H); 13 CNMR (100 MHz, CD 3 ): 151.1, 130.1, 129.9, 120.6(q, J = 280Hz),118.3, 85.4(q, J = 40 Hz); MS (EI):244(M +, 28.00), 127(100), 99(57.20), 111(42.98), 75(33.25), 129(31.91); HRMS (EI) M + calcd for C 8 H 5 F 3 O 2 :243.9670, found 243.9672; IR (KBr) ν/cm -1 : 2959, 1749, 1589, 1490, 1383, 1289, 1267, 1222, 1174, 1095. 1-bromo-2-(1-chloro-2,2,2-trifluoroethoxy)benzene (2m) Colorless oil 19 FNMR (282 MHz, CD 3 ):-80.3(d, J = 4 Hz); 1 HNMR (400 MHz, CD 3 ):7.61(d, J = 8 Hz,1H),7.34(t, J = 8 Hz,1H), 7.18(d,J = 8 Hz, 1H), 7.08(t, J = 8 Hz,1H), 6.13(q, J = 4 Hz,1H); 13 CNMR (100MHz, CD 3 ):151.1, 134.2, 128.6, 126.3, 120.6(q,J = 280Hz), 118.4, 113.9, 85.9(q, J = 40 Hz); MS (EI):290(M +, 100), 171(95.71), 173(93.70), 288(76.16), 143(68.10); HRMS (EI) (M-H) + calcd for C 8 H 5 F 3 OBr:287.9164, found 287.9168; IR (KBr) ν/cm -1 :3071, 2963, 1579, 1477, 1445, 1381, 1292, 1263, 1231, 1194, 1150. 2) General procedure fo r Copper-mediated radical cro ss-coupling between HCFC-123 and thiophenols. S9

A 20 ml sealed tube was charged with Cu powder (8.5 mmol, 0.544 g) and filled with N 2. HCFC-123(10 ml), p-tolsh (3a, 5 mmol, 0.620 g), Et 3 N (6.25 mmol, 627 mg) and Et 2 NH (15 mmol, 1.096 g) were added into this sealed tube. The solution in the sealed tube was stirred at 75 o C for 24 h. After the solution was cool, the mixture was poured into Et 2 O (50 ml). The precipitation was removed with filtration. The solvent was removed and the residue was purified by flash chromatography on a silica gel column using PE:DCM = 20:1 as the eluent. 4a was obtained as the colorless oil (0.948 g, 79% yield). (1-chloro-2,2,2-trifluoroethyl)(p-tolyl)sulfane 1 (4a) Colorless oil 19 FNMR (282 MHz, CD 3 ):-72.4(d, J = 6.6 Hz); 1 HNMR (400 MHz, CD 3 ):2.37(s, 3H), 5.21(q, J = 6.4 Hz, 1H), 7.20(d, J = 8 Hz,2H), 7.50(d, J = 8 Hz,2H). (1-chloro-2,2,2-trifluoroethyl)(4-isopropylphenyl)sulfane (4b) Colorless oil 19 FNMR (282 MHz, CD 3 ):-72.5(d, J = 7 Hz); 1 HNMR (400 MHz, CD 3 ):7.53(d, J = 8.4 Hz, 2H), 7.25(d, J = 8.4 Hz,2H), 5.22(q, J = 6.3 Hz,1H), 2.87-2.97(m,1H), 1.25(d, J = 7 Hz, 6H); 13 CNMR (100 MHz, CD 3 ):151.3, 135.1, 127.6,126.2, 122.8(q, J = 280 Hz), 65.8 (q, J = 35 Hz), 33.9, 23.6; S10

MS (EI):268(M +, 49.46), 253(100), 255(38.31), 136(26.69), 270(18.83), 135(15.19); HRMS (EI) M + calcd for C 11 H 12 F 3 S:268.0296, found 268.0304; IR (KBr) ν/cm -1 :2965, 2932, 2873, 1595, 1488, 1460, 1303, 1254, 1171, 1115. (1-chloro-2,2,2-trifluoroethyl)(4-methoxyphenyl)sulfane (4c) S CF 3 O Colorless oil 19 FNMR (282 MHz, CD 3 ):-72.3(d, J = 5 Hz); 1 HNMR (400 MHz, CD 3 ):7.56(d, J = 8.4 Hz,2H), 6.92(d, J = 8.4 Hz,2H), 5.15(q, J = 6.6 Hz,1H), 3.83(s, 3H) 13 CNMR (100 MHz, CD 3 ):160.4, 136.4, 121.8(q, J = 279 Hz), 118.3, 113.9, 64.6(m), 54.3; MS (EI):256(M +, 53.63), 139(100), 258(20.90), 95(16.50), 140(16.43), 96(15.52); HRMS (EI) M + calcd for C 9 H 8 F 3 SO:255.9936, found 255.9939; IR (KBr) ν/cm -1 :2967, 2840, 1593, 1495, 1304, 1292, 1250, 1173, 1115. N-(4-(1-chloro-2,2,2-trifluoroethylthio)phenyl)acetamide (4d) S CF 3 AcHN White solid 19 FNMR (282 MHz, CD 3 ):-72.3(d, J = 6 Hz); 1 HNMR (400 MHz, CD 3 ):7.55(br, 4H), 7.46(br, 1H), 5.17(q, J = 6.4 Hz,1H), 2.17(s, 3H); 13 CNMR (100 MHz, DMSO):169.2, 141.6, 136.2, 123.6(q, J = 279Hz), 121.1, 120.0, 64.0(q, J = 34 Hz), 24.5; MS (EI):283(M +, 4.51), 79(100), 124(92.30), 78(61.15), 51(47.37), 52(34.64); HRMS (EI) M + calcd for C 10 H 9 NOF 3 S:283.0045, found 283.0046; S11

IR (KBr) ν/cm -1 :3318, 1678, 1592, 1537, 1495, 1396, 1304, 1257, 1106. (2-bromophenyl)(1-chloro-2,2,2-trifluoroethyl)sulfane (4e) Colorless oil 19 FNMR (282 MHz, CD 3 ):-72.6(d, J = 5.7 Hz); 1 HNMR (400 MHz, CD 3 ):7.69-7.71(m, 2H), 7.27-7.39(m, 2H), 5.42(q, J = 6.2 Hz,1H); 13 CNMR (100 MHz, CD 3 ):136.2, 133.9, 131.3, 130.8, 129.0, 128.3, 125.6(q, J = 280 Hz), 63.9(m); MS (EI):306(M +, 49.00), 108(100), 190(55.46), 304(36.23), 189(30.45), 269(28.85); HRMS (EI) M + calcd for C 8 H 5 F 3 SBr:303.8936, found 303.8941; IR (KBr) ν/cm -1 :3063, 2970, 1449, 1305, 1252, 1172, 1115, 1022, 809, 745. (2-bromophenyl)(2,2,2-trifluoroethyl)sulfane (4 e) Colorless oil 19 FNMR (282 MHz, CD 3 ):-66.1(t, J = 9.3 Hz); 1 HNMR (400 MHz, CD 3 ):7.43-7.52(m, 2H), 7.06-7.21(m, 2H), 3.38(q, J = 9.8 Hz, 2H); 13 CNMR (100 MHz, CD 3 ):134.1, 133.5, 133.0, 129.3, 128.0, 126.7, 125.4(q, J = 275 Hz), 36.6(q, J = 33 Hz); MS (EI):272(M +, 100), 270(93.01), 122(92.25), 108(79.36), 203(33.73), 201(33.58); HRMS (EI) M + calcd for C 8 H 6 F 3 SBr:269.9326, found 269.9329; S12

IR (KBr) ν/cm -1 :3062, 2947, 1450, 1309, 1269, 1240, 1130, 1080, 750. (4-chlorophenyl)(2,2,2-trifluoroethyl)sulfane (4f) 1 19 FNMR (282 MHz, CD 3 ):-72.2(d, J = 8 Hz); 1 HNMR (300 MHz, CD 3 ):7.56(d, J = 8 Hz, 2H), 7.38(d, J = 8 Hz,2H), 5.22(q, J=6.4 Hz, 1H); 2-(1-chloro-2,2,2-trifluoroethylthio)pyridine (4g) 1 19 FNMR (282 MHz, CD 3 ):-72.5(d,J = 6 Hz) 1 HNMR (300 MHz, CD 3 ):8.52(d, J = 5 Hz,1H), 7.59-7.68(m,1H),7.15-7.27(m,2H), 6.41(q, J = 7 Hz,1H). 2-(2,2,2-trifluoroethylthio)pyridine (4 g) 19 FNMR (282 MHz, CD 3 ):-66.1(t, J = 9.3 Hz); 1 HNMR (400 MHz, CD 3 ):8.46(d, J = 4.5 Hz,1H), 7.53-7.57(m, 1H), 7.24-7.27(m, 1H), 7.06-7.09(m, 1H), 4.06(q, J = 9.8 Hz, 2H); 13 CNMR (100 MHz, CD 3 ):154.5, 149.3, 136.5, 125.3(q, J = 275 Hz), 122.3, 120.5, 31.1(q, J = 33Hz); MS (EI):193(M +, 87.38), 79(100), 122(92.25), 124(77.64), 173(74.18), 78(51.22); HRMS (EI) M + calcd for C 7 H 6 F 3 SN:193.0173, found 193.0172; IR (KBr) ν/cm -1 :3052, 3000, 2946, 1580, 1560, 1456, 1418, 1308, 1273, 1243, 1119. S13

3) Synthesis of difluoroviny aryl ether from 2 2equivZn Ar OCHCF 3 DMSO ArO 2 110 o Cfor3h 5 F F A 10mL schlenk tube was charged with Zn (10 mmol, 0.650 g) and filled with N 2, then nitrogen purged solvent DMSO (10 ml) and 2e (5 mmol, 1.305 g)was added. The mixture was stirred at 110 o C for about 3 h detected by TLC. After the reaction was over, the mixture was poured into Et 2 O (50 ml). The resulted solution was washed with was water and dried over Na 2 SO 4. The solvent was removed and the residue was purified by flash chromatography on a silica gel column using PE as the eluent. 5e was obtained as colorless oil (0.948 g, 92% yield). 1-(2,2-difluorovinyloxy)-4-methoxybenzene (5a) Colorless oil 19 FNMR (282 MHz, CD 3 ):-100.8(dd, J = 72, 14 Hz,1F), -118.7(d,J = 72 Hz,1F); 1 HNMR (400 MHz, CD 3 ):6.93(d, J = 9 Hz,2H),6.83(d, J= 8 Hz,2H), 6.00(dd, J = 14, 3 Hz, 1H), 3.76(s, 3H); 13 CNMR (100 MHz, CD 3 ):156.6(dd, J = 290, 278 Hz), 155.4, 151.1, 116.4, 114.7,105.3(dd, J = 55, 15 Hz), 55.6. MS (EI):186(M +, 100), 171(44.14), 157(39.51), 123(37.87), 77(24.12); HRMS (EI) M + calcd for C 9 H 8 F 2 O 2 :186.0492, found 186.0494; IR (KBr) ν/cm -1 :3058, 3005, 2838, 1770, 1507, 1348, 1241, 1226, 1134,1036. 1-(2,2-difluorovinyloxy)naphthalene (5e) S14

O F F Colorless oil 19FNMR (282 MHz, CD3):-97.7(dd, J = 68, 14 Hz, 1F), -115.6(d, J = 68 Hz, 1F); 1 HNMR (400 MHz, CD 3 ):8.27-8.29(m,1H), 7.83-7.86(m,1H),7.53-7.58(m,3H),7.39(t, J = 8 Hz, 1H), 6.97(d, J = 8 Hz,1H), 6.24(dd, J = 15, 5 Hz,1H); 13 CNMR (CD 3 ):156.9(dd, J = 291, 279 Hz), 153.0, 134.0, 127.5, 126.8, 125.9, 125.4, 125.0, 122.7, 121.6, 107.1, 104.6(dd, J = 56, 15 Hz); MS (EI):206(M +, 100), 127(58.31), 177(57.25), 186(23.03), 126(21.92),128(17.13); HRMS (EI) M + calcd for C 12 H 8 F 2 O:206.0543, found 206.0542; IR (KBr) ν/cm -1 :3060, 1769, 1597, 1579, 1511, 1463, 1395, 1342, 1246, 1185. 2-(2,2-difluorovinyloxy)-1-isopropyl-4-methylbenzene (5f) Colorless oil 19FNMR (282 MHz, CD3):-99.0(dd, J = 73, 16 Hz, 1F), -117.0(d, J = 73 Hz, 1F); 1 HNMR (400 MHz, CD 3 ):7.15(d, J = 8 Hz,1H), 6.88(d, J = 8 Hz,1H), 6.77(s,1H), 6.05(dd, J = 15, 3 Hz,1H), 3.27-3.34(m,1H), 3.24(s, 3H), 1.24(d, = 7 Hz,6H); 13 CNMR (100 MHz, CD 3 ):156.6(dd, J = 290, 278 Hz), 154.3, 136.6, 134.3, 126.5, 123.6, 114.2, 104.8(dd, J = 55, 15 Hz), 26.7, 22.7, 21.0; MS (EI):212(M +, 100), 177(91.04), 197(61.59), 91(56.50), 115(41.24),105(35.59); HRMS (EI) M + calcd for C 12 H 14 F 2 O:212.1013, found 212.1017; IR (KBr) ν/cm -1 :2964, 2929, 2872, 1769, 1617, 1507, 1416, 1347, 1420, 1177, 1138. S15

methyl 4-(2,2-difluorovinyloxy)benzoate (5j) White solid m.p.:32.2-33.1 ; 19 FNMR (282 MHz, CD3):-96.0(dd, J = 66, 16 Hz, 1F), -114.4(d, J = 66 Hz, 1F); 1 HNMR (400 MHz, CD 3 ):8.00(d, J = 9 Hz,2H), 7.01(d, J = 9 Hz,2H), 6.00(dd, J = 15, 3 Hz,1H), 3.87(s, 3H); 13 CNMR (100MHz, CD 3 ):166.4, 160.5, 156.7(dd, J = 291, 279 Hz), 131.7, 124.8, 114.8, 103.9(dd, J = 56, 16 Hz), 52.0; MS (EI):214(M +, 45.89), 189(100), 127(14.59), 136(11.81), 155(10.56), 184(10.11); HRMS (EI) M + calcd for C 10 H 8 F 2 O 3 :214.0442, found 214.0441; IR (KBr) ν/cm -1 :3067, 2955, 1770, 1722, 1606, 1506, 1436, 1283, 1251, 1168, 1112. 1-bromo-2-(2,2-difluorovinyloxy)benzene (5m) Br F O F Colorless oil 19 FNMR (282 MHz, CD3): -97.0(dd, J = 66, 16 Hz, 1F), -115.4(d, J = 66 Hz, 1F); 1 HNMR (400 MHz, CD 3 ):8.00(d, J = 9 Hz,2H), 7.01(d, J = 9 Hz, 2H), 6.00(dd, J = 15, 3 Hz,1H); 13 CNMR (100 MHz, CD 3 ): 156.8(dd, J = 290, 279 Hz), 153.7, 133.8, 128.5, 124.2, 114.9, 111.8, 104.6(dd, J = 57, 16 Hz); MS (EI):234(M +, 61.30), 127(100), 155(93.24), 236(61.41), 75(38.97),76(37.63); HRMS (EI) M + calcd for C 8 H 5 F 2 OBr:233.9492, found 233.9494; IR (KBr) ν/cm -1 :3066, 1769, 1588, 1506, 1475, 1444, 1351, 1250, 1143,930. S16

4) Trapping the radical intermediate with styrene 2 mmol 3mmolCu 3mmolEt 2 NH HCFC-123 75 o Cfor3h CF 3 6 97% ioslated yield, dr = 2:1 A 10mL sealed tube with charged with Cu powder (3 mmol, 0.192 g) and filled with N 2. HCFC-123 (4 ml), styrene (2 mmol, 0.208 g) and Et 2 NH (10 mmol, 0.731 g) were added into this sealed tube. The solution in the sealed tube was stirred at 75 o C for 3 h. After the solution was cool, the mixture was poured into Et 2 O (50 ml). The precipitation was removed with filtration. The solvent was removed and the residue was purified by flash chromatography on a silica gel column using PE as the eluent. 6 was obtained as the colorless oil (0.497 g, 97% yield). (1,3-dichloro-4,4,4-trifluorobutyl)benzene (6) Colorless oil 19 FNMR (282 MHz, CD3):-74.8(d, J = 7.6 Hz, 0.66*3F), -75.0(d, J =6.3 Hz, 0.32* 3F); 1 HNMR (400 MHz, CD 3 ):7.35-7.41(m, 5H), 5.18(dd, J = 11.4, 1.8 Hz, 0.66H), 5.10(dd, J = 10, 5.3 Hz, 0.32H), 4.59-4.64(m, 0.67H), 3.66-3.70(m, 0.32H), 2.67-2.77(m, 1.4H), 2.29-2.36(m, 0.7H); 13 CNMR (100 MHz, CD 3 ):139.9, 138.3, 129.3, 129.2, 129.0, 128.9, 127.1, 126.8, 123.9(q, J = 279 Hz), 123.6(q, J = 279 Hz), 59.1, 57.9, 55.4(q, J = 34 Hz), 54.5(q, J = 34 Hz), 41.4; MS (EI):234(M +, 19.70), 221(100), 125(51.08), 91(44.30), 223(36.58), 104(20.30); HRMS (EI) M + calcd for C 10 H 9 F 3 2 :256.0033, found 256.0029; IR (KBr) ν/cm -1 :3035, 2927, 1495, 1456, 1313, 1268, 1189, 1165, 1127, 1025, 939. S17

3, 19 F, 1 H and 13 C NMR spectra for new compounds S18

-80.065-80.080 O 2a O CF 3 0-50 -100-150 PPM 7.079 7.057 6.910 6.887 6.042 6.032 6.022 6.012 3.801 O CF 3 O 2a 3.27 2.21 2.03 1.00 15 10 5 0 PPM S19

156.841 148.686 125.028 122.196 119.409 118.657 118.348 116.625 114.925 114.812 98.724 87.557 87.168 86.785 86.398 77.314 76.996 76.678 55.592 O CF 3 O 2a 250 200 150 100 50 0 PPM S20

-80.067-80.081 O CF 3 AcHN 2b 0-50 -100-150 PPM 9.962 7.593 7.571 7.296 7.285 7.141 7.119 3.296 2.002 O CF 3 AcHN 2b 3.03 2.01 1.98 1.00 1.01 15 10 5 0 PPM S21

168.630 149.308 149.168 136.571 120.811 117.567 98.729 98.715 85.895 85.515 40.578 40.364 40.301 40.158 39.949 39.736 39.533 39.320 24.307 O CF 3 AcHN 2b 250 200 150 100 50 0 PPM S22

-80.852-80.867 O CF 3 2c 0-50 -100-150 PPM 7.410 7.391 7.370 7.243 7.211 7.191 7.174 7.130 7.110 6.138 6.127 6.117 6.107 1.532 0.084 0.006 O CF 3 2c 2.04 2.01 1.03 1.00 0.00 12 10 8 6 4 2 0PPM

154.684 129.992 129.820 124.970 124.790 122.191 119.408 116.860 116.623 116.376 98.719 86.042 85.648 85.254 84.868 77.300 76.982 76.664 O CF 3 2c 250 200 150 100 50 0 PPM S24

-80.339-80.353 F 3 C O 2d 0-50 -100-150 PPM 7.113 7.093 6.916 6.901 6.121 6.111 2.362 2.244 O CF 3 2d 3.14 3.03 2.00 1.04 1.00 15 10 5 0 PPM S25

153.028 137.223 131.338 125.535 125.254 122.312 119.525 115.475 86.268 85.879 85.490 77.299 76.981 76.659 21.128 15.398 F3C O 2d 250 200 150 100 50 0 PPM S26

-79.885-79.900 8.199 8.190 8.177 7.865 7.849 7.843 7.679 7.658 7.563 7.554 7.548 7.540 7.459 7.440 7.419 7.243 7.196 7.176 6.317 6.317 6.307 6.307 O CF 3 2e 0.00 1.00 1.02 1.01 0.98 0.97 1.03 1.82 15 10 5 0 PPM O CF 3 2e 0-50 -100-150 PPM S27

150.559 149.171 134.685 127.676 127.090 126.527 125.611 125.174 124.595 122.367 121.356 119.580 109.320 98.719 86.159 85.769 85.376 84.928 77.309 76.990 76.672 O CF 3 2e 250 200 150 100 50 0 PPM S28

-80.067-80.081 O CF 3 2f 0-50 -100-150 PPM 7.243 7.199 7.179 6.975 6.956 6.895 6.167 6.157 6.147 3.319 3.301 3.285 3.267 3.249 2.360 1.528 1.232 1.214 1.207 1.190 0.008 O CF 3 6.38 2f 0.00 1.02 0.99 1.00 1.02 3.14 1.01 15 10 5 0 PPM S29

151.760 136.965 135.845 126.978 125.370 122.362 119.577 114.743 86.138 85.752 85.357 84.973 77.294 76.977 76.660 26.437 22.882 22.658 21.115 O CF 3 2f 250 200 150 100 50 0 PPM S30

-80.019-80.033 O 2 N O CF 3 2g 0-50 -100-150 PPM 8.068 8.048 7.970 7.607 7.585 7.565 7.467 7.464 7.447 7.446 7.443 6.208 6.199 6.188 6.180 O 2 N O CF 3 2g 0.95 0.95 1.01 0.97 1.00 15 10 5 0 PPM S31

154.635 149.173 149.161 130.833 123.189 121.895 119.591 119.107 111.773 98.720 85.108 84.712 84.315 83.914 77.304 76.988 76.670 O 2 N O CF 3 2g 250 200 150 100 50 0 PPM S32

-80.251-80.265 F 3 C O 2h CN 0-50 -100-150 PPM 7.697 7.675 7.244 7.200 7.178 6.185 6.179 6.176 6.172 1.106-0.031 O CF 3 NC 2h 1.94 2.04 1.00 15 10 5 0 PPM S33

157.165 134.340 121.897 119.111 118.026 117.201 108.403 98.724 84.376 83.979 83.580 83.185 77.349 77.027 76.710 F 3 C O 2h CN 160 140 120 100 80 PPM S34

-80.139-80.153 O CF 3 OHC 2i 0-50 -100-150 PPM 9.944 7.924 7.902 7.240 7.218 6.224 6.214 O CF 3 OHC 2i 2.07 2.13 1.00 1.01 15 10 5 0 PPM S35

190.454 158.600 132.903 131.920 121.978 119.192 116.728 84.474 84.076 83.679 83.283 77.320 76.998 76.680 F 3 C O 2i CHO 250 200 150 100 50 0 PPM S36

-79.922-79.942 N O CF 3 2k 0-50 -100-150 PPM 8.490 8.442 7.446 7.425 7.329 6.155 6.147 6.139 N O CF 3 2k 2.01 2.00 1.00 15 10 5 0 PPM S39

151.141 146.044 139.695 124.249 124.108 122.079 119.082 116.317 85.461 85.354 85.262 84.866 84.471 77.333 77.015 76.696 N O CF 3 2k 250 200 150 100 50 0 PPM S40

-80.900-80.915 7.352 7.329 7.061 7.039 6.066 6.056 6.047 6.037 2l O CF 3 2.11 2.16 1.00 15 10 5 0 PPM O CF 3 2l 0-50 -100-150 PPM S41

153.128 130.199 129.986 124.822 122.041 119.256 118.321 116.439 86.007 85.614 85.221 84.826 77.289 76.972 76.654 O CF 3 2l 250 200 150 100 50 0 PPM S42

-80.347-80.361 F 3 C O Br 2m 0-50 -100-150 PPM 7.623 7.603 7.362 7.342 7.323 7.207 7.187 7.103 7.084 7.064 6.140 6.131 6.123 F 3 C O Br 2m 0.90 1.02 1.01 1.10 1.00 15 10 5 0 PPM S43

151.152 134.237 128.696 126.377 122.045 119.253 118.430 113.942 86.130 85.737 77.299 76.981 76.664 F3C O Br 2m 250 200 150 100 50 0 PPM S44

-72.482-72.503 S CF 3 4b 0-50 -100-150 PPM 7.544 7.524 7.262 7.241 5.244 5.228 5.212 5.195 2.942 2.925 2.908 1.529 1.259 1.241-0.004 SCHCF 3 4b 6.37 1.92 2.20 0.95 1.00 15 10 5 0 PPM S45

151.362 135.114 127.665 126.213 124.210 121.430 98.724 77.299 76.981 76.659 66.432 66.081 65.733 65.382 33.917 23.733 23.652 SCHCF 3 4b 250 200 150 100 50 0 PPM S46

-72.289-72.308 S CF 3 4c O 60-65 -70-75 -80 PPM 7.569 7.539 7.252 6.925 6.896 5.181 5.160 5.138 5.115 3.921 3.826 1.588-0.000 S O CF 3 4c 3.32 1.90 2.00 0.85 12 10 8 6 4 2 0 PPM S47

160.402 136.601 136.501 136.439 136.222 136.124 130.350 125.977 123.203 120.419 118.359 114.055 113.922 113.884 113.809 76.290 75.973 75.655 65.212 65.084 64.860 64.730 64.517 64.387 54.462 54.392 54.289 54.213 S O CF 3 4c 200 150 100 50 0 PPM S48

-72.307-72.329 S CF 3 4d NHAc 0-50 -100-150 PPM 7.550 7.460 7.243 5.194 5.179 5.163 5.146 2.178 1.657-0.023 S CF 3 4d NHAc 3.97 3.07 0.93 1.00 14 12 10 8 6 4 2 0 PPM S49

169.214 141.652 136.241 122.265 125.041 121.168 120.017 64.785 64.231 63.896 63.461 40.668 40.460 40.253 40.037 39.833 39.624 39.409 24.544 S NHAc CF 3 4d 200 150 100 50 0 PPM S50

-72.665-72.685 Br S CF 3 4e 0-50 -100-150 PPM 7.706 7.704 7.699 7.696 7.686 7.683 7.680 7.380 7.361 7.342 7.339 7.303 7.299 7.283 7.264 7.260 7.252 5.433 5.417 5.401 5.384 1.552-0.000 Br S CF 3 4e 2.16 1.92 1.00 14 12 10 8 6 4 2 0 PPM S51

135.192 135.133 132.925 132.865 130.338 130.310 130.262 130.201 130.176 129.845 128.009 127.359 127.301 126.000 123.220 120.434 76.284 75.971 75.655 63.462 63.398 63.109 63.042 62.758 62.685 62.329 Br S CF 3 4e 200 150 100 50 0 PPM S52

-66.156-66.189-66.222 Br F 3 C S 4'e 0-50 -100-150 PPM 7.652 7.632 7.576 7.558 7.339 7.335 7.320 7.300 7.207 7.203 7.188 7.169 3.549 3.524 3.500 3.475 1.585 Br F 3 C S 4'e 1.95 2.10 2.00 14 12 10 8 6 4 2 0 PPM S53

133.080 132.501 132.433 132.002 131.924 128.577 128.555 128.378 128.314 127.034 126.994 126.893 125.711 125.681 125.611 122.865 120.112 76.295 76.235 75.974 75.650 36.129 35.855 35.804 35.747 35.515 35.476 35.427 35.149 35.101 Br F 3 C S 4'e 200 150 100 50 0 PPM S54

-66.979-67.014-67.050 F 3 C S 4'g N 0-50 -100-150 PPM 8.473 8.462 7.573 7.554 7.534 7.531 7.278 7.265 7.245 7.094 7.079 7.076 7.063 4.101 4.077 4.052 4.027 1.747 0.018 F 3 C S N 4'g 2.00 1.18 0.98 1.02 0.99 10 5 0 PPM S55

154.566 149.329 149.265 136.528 136.454 126.727 123.989 122.377 120.551 120.463 77.280 76.967 76.651 31.483 31.148 30.812 30.481 F 3 C S N 4'g 200 150 100 50 0 PPM S56

-100.611-100.666-100.866-100.915-118.591-118.837 6.947 6.924 6.849 6.826 6.018 6.010 5.980 5.972 3.786 3.768 O F F O 5a 1.00 3.34 1.91 2.06 15 10 5 0 PPM O F F O 5a 0-50 -100-150 PPM S57

159.437 156.672 156.548 155.412 153.784 151.157 118.655 116.401 114.917 114.708 105.652 105.502 105.100 104.948 77.335 77.017 76.698 55.664 55.624 O F F O 5a 250 200 150 100 50 0 PPM S58

-95.858-95.915-96.092-96.137-114.320-114.539 8.014 7.992 7.028 7.006 6.129 6.120 6.092 6.083 3.877 O F F MeOOC 5j 3.27 2.09 2.08 1.00 15 10 5 0 PPM MeOOC O 5j F F 0-50 -100-150 PPM S59

166.413 160.536 159.591 156.806 156.688 153.903 131.733 124.896 114.858 104.240 104.085 103.677 103.522 77.339 77.021 76.702 52.047 O F F MeOOC 5j 250 200 150 100 50 0 PPM S60

-97.580-97.628-97.815-97.869-115.522-115.768 8.297 8.282 8.274 7.861 7.853 7.848 7.838 7.580 7.556 7.547 7.540 7.531 7.410 7.391 7.370 6.982 6.963 6.266 6.258 6.229 6.219 O F F 5e 0.96 3.02 0.98 1.08 1.02 1.00 15 10 5 0 PPM O F F 5e 0-50 -100-150 PPM S61

159.742 156.968 156.847 154.077 153.013 134.635 127.586 126.851 125.943 125.426 125.096 122.756 121.652 107.191 105.029 104.882 104.473 104.322 77.373 77.056 76.738 O F F 5e 250 200 150 100 50 0 PPM S62

-98.904-98.959-99.159-99.208-116.884-117.130 7.267 7.165 7.145 6.892 6.873 6.770 6.075 6.067 6.037 6.028 3.346 3.329 3.311 3.294 3.277 2.343 1.566 1.250 1.233 0.027 O F F 5f 0.98 0.97 0.95 0.95 1.00 6.20 3.08 15 10 5 0 PPM 5f F O F 0-50 -100-150 PPM S63

159.451 156.684 156.559 154.306 153.797 149.186 136.662 134.388 126.511 123.693 114.262 105.244 105.094 104.690 104.541 98.737 98.722 77.330 77.013 76.924 76.695 76.617 48.294 22.707 26.712 22.586 22.547 22.520 21.079 21.030 O F F 5f 250 200 150 100 50 0 PPM S64

-96.841-96.898-97.075-97.120-115.303-115.522 7.556 7.537 7.279 7.258 7.240 7.236 7.002 6.981 6.956 6.937 6.917 6.074 6.064 6.036 6.028-0.024 Br O F F 5m 1.99 1.18 1.00 0.96 14 12 10 8 6 4 2 0 PPM Br O F F 5m 0-50 -100-150 PPM S65

159.661 156.876 156.747 153.969 153.701 133.810 128.511 124.243 114.962 111.897 105.018 104.863 104.451 104.298 77.302 76.983 76.659 Br F O F 5m 200 150 100 50 0 PPM S66

-74.846-74.873-75.017-75.040 CF 3 6-72 -74-76 -78-80 -82 PPM 7.419 7.405 7.384 7.379 7.371 7.362 7.351 7.261 5.203 5.199 5.175 5.170 5.122 5.109 5.097 5.084 4.643 4.638 4.626 4.622 4.615 4.609 4.598 4.593 3.700 3.693 3.684 3.673 3.667 2.776 2.767 2.750 2.743 2.709 2.701 2.684 2.677 2.672 2.362 2.356 2.333 2.327 2.319 2.296 2.290 1.560 0.091 0.015 5.00 CF 3 6 1.40 0.66 0.32 0.67 0.32 0.00 0.70 10 5 0 PPM S67

139.930 138.379 129.376 129.292 129.257 129.212 129.011 128.995 128.733 128.132 127.802 127.120 127.074 126.852 126.807 126.533 125.358 125.034 122.584 122.260 119.819 119.477 77.339 77.213 77.014 76.699 59.180 57.926 55.908 55.572 55.237 55.013 54.901 54.676 54.339 53.998 41.239 41.226 41.196 40.999 1.024-0.017 CF 3 6 200 150 100 50 0 PPM S68

4, Reference 1, Pustovit, Y.; Alexeenko, A.; Trofymchuk, S.; Lukin, O.; Tolmachev, A. A. Synthesis, 2010, 1159. S69