Supporting Information for. Catalytic C H α-trifluoromethylation of α,β-unsaturated Carbonyl Compounds

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1 Supporting Information for Catalytic C H α-trifluoromethylation of α,β-unsaturated Carbonyl Compounds Zhongxue Fang, a Yongquan Ning, a Pengbing Mi, a Peiqiu Liao, a Xihe Bi* a,b a Department of Chemistry, Northeast Normal University, Changchun , China. b State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin , China. bixh507@nenu.edu.cn Contents I. General information..s2 II. Synthesis and spectra data of compounds 3, 5, 7 and drug derivatives..s2-s7 III. Crystallography..S8-S13 IV. NMR spectra copies S14-S47 S1

2 I. General information All reagents were purchased from commercial sources and used without treatment, unless otherwise indicated. The products were purified by column chromatography over silica gel. 1 H-NMR, 13 C-NMR and 19 F NMR spectra were recorded at 25 ºC on a Varian 500 MHz, 125 MHz and MHz, respectively, and TMS was used as internal standard. Mass spectra were recorded on BRUKER AutoflexIII Smartbeam MS-spectrometer. High resolution mass spectra (HRMS) were recorded on Bruck microtof by using ESI method. II. Synthesis and spectra data of compounds 3, 5, 7 and drug derivatives Typical synthetic procedure (with 3a as an example): Togni reagent (474 mg, 1.5 mmol) and CuI (19 mg, 0.1 mmol) was added into a flame-dried vial with a magnetic stir bar, and then sealed with a septum. After the vial was evacuated and backfilled with N 2 for three times, 2a (238 mg, 1.0 mmol) in DMF (2.0 ml) was then added via syringe. The reaction mixture was heated to 80 o C and stirred for 26 h until the disappearance of substrate 2a as indicated by TLC. The resulting mixture was concentrated and the residue was taken up in DCM. The organic layer was washed with brine, dried over MgSO 4 and concentrated. Purification of the crude product by flash column chromatography (silica gel, petroleum ether: ethyl acetate = 100:1) to afford the product 3a (238 mg, 78%) as yellowish liquid. (3a) Yellowish liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 2H), 7.52 (t, J = 7.5 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), 3.72 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 193.1, 161.0, (q, J = 5.9 Hz), 135.5, 134.2, 131.5, 129.6, 128.7, (q, J = 30.0 Hz),124.4, (q, J = Hz), 114.1, 55.2; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 17 H 14 F 3 O 2 [M+H] + : , found (3b) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 2H), 7.51 (t, J = 7.5 Hz, 1H), 7.44 (s, 1H), 7.37 (m, J = 7.5 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.93 (d, J = 8.0 Hz, 2H), 2.24 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 192.9, 140.6, (q, J = 5.9 Hz), 135.4, 134.2, , , 129.4, 129.1, 128.7, (q, J = 30.0Hz), (q, J = Hz), 21.3; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 17 H 14 F 3 O [M+H] + : , found S2

3 (3c) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.89 (d, J = 8.0 Hz, 2H), 7.54 (t, J = 7.5 Hz, 1H), 7.43 (s, 1H), 7.39 (t, J = 7.5 Hz, 2H), (m, 4H); 13 C-NMR (CDCl 3, 125 MHz) δ 192.3, 136.2, (q, J = 5.9 Hz), 135.1, 134.5, 130.7, 130.3, 129.5, 129.0, 128.9, 128.8, (q, J = Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 11 ClF 3 O [M+H] + : , found O F 3 C Ph F (3d) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.89 (d, J = 8.0 Hz, 2H), 7.53 (t, J = 7.5 Hz, 1H), 7.45 (s, 1H), 7.37 (t, J = 8.0 Hz, 2H), (m, 2H), 6.88 (t, J = 8.5 Hz, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 192.5, (d, J = Hz), (q, J = 6.0 Hz), 135.2, 134.4, (d, J = 8.5 Hz), 129.5, 128.8, (d, J = 3.5 Hz), (q, J = Hz), (d, J = 21.8 Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F), (m, 1F); HRMS (ESI) m/z calculated for C 16 H 11 F 4 O [M+H] + : , found (3e) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 8.02 (d, J = 7.5 Hz, 2H), 7.62 (t, J = 7.5 Hz, 1H), 7.50 (s, 1H), 7.46 (t, J = 7.5 Hz, 1H), 7.32 (d, J = 5.0 Hz, 1H), 7.14 (d, J = 3.5 Hz, 1H), (m, 1H); 13 C-NMR (CDCl 3, 125 MHz) δ 192.3, 135.5, 134.7, 134.5, 132.8, 130.7, 129.7, 128.9, (q, J = 6.3 Hz), 127.6, (q, J = 31.0 Hz), (q, J = Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 14 H 10 F 3 OS [M+H] + : , found (3f) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 7.36 (t, J = 7.5 Hz, 2H), (m, 2H), (m, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 192.6, (q, J = 5.9 Hz), 135.4, 134.2, 131.9, 130.1, 129.6, 129.5, 128.8, 128.7, 128.6, (q, J = 272.9, Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 12 F 3 O [M+H] + : , found S3

4 (3g) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.82 (d, J = 8.5 Hz, 2H), 7.52 (s, 1H), 7.34 (d, J = 8.5 Hz, 2H), (m, 5H); 13 C-NMR (CDCl 3, 125 MHz) δ 191.4, 140.9, (q, J = 5.9 Hz), 133.7, 131.7, 130.8, 130.3, 129.4, 129.1, 128.8, (q, J = 30.0 Hz), (q, J = Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 11 ClF 3 O [M+H] + : , found (3h) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.89 (d, J = 9.0 Hz, 2H), 7.42 (s, 1H), (m, 2H), (m, 3H), 6.84 (d, J = 9.0 Hz, 2H), 3.80 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 190.9, 164.5, (q, J = 5.9 Hz), 132.1, 130.0, 129.5, (q, J = 29.0 Hz), 128.6, 128.5, (q, J = Hz), 114.0, 55.4; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 17 H 14 F 3 O 2 [M+H] + : , found (3i) Yellow solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.84 (d, J = 8.5 Hz, 2H), 7.43 (s, 1H), (m, 5H), 6.79 (d, J = 8.0 Hz, 2H), 6.03 (s, 1H); 13 C-NMR (CDCl 3, 125 MHz) δ 191.5, 161.5, (q, J = 5.8 Hz), 132.7, 132.6, 131.9, 130.1, 129.5, 128.7, 128.5, 128.4, (q, J = Hz), 115.7; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 12 F 3 O 2 [M+H] + : , found (3j) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 1H), 7.53 (d, J = 3.5 Hz, 1H), 7.46 (s, 1H), (m, 2H), (m, 3H), (m, 1H); 13 C-NMR (CDCl 3, 125 MHz) δ 184.2, 142.9, (q, J = 5.8 Hz), 136.3, 135.6, 132.0, 130.2, 129.5, 128.9, 128.7, 128.4, (q, J = 272.8); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 14 H 10 F 3 OS [M+H] + : , found O F 3 C Ph S4

5 (3k) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 2H), 2.21 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 199.2, (q, J = 6.0 Hz), 132.2, (q, J = 30.0 Hz), 131.4, 130.4, 129.1, 128.9, (q, J = Hz), 31.1; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 11 H 10 F 3 O [M+H] + : , found (3l) Yellow solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 2H), 7.30 (s, 1H); 13 C-NMR (CDCl 3, 125 MHz) δ 183.4, 179.6, (q, J = 6.0 Hz), (q, J = 30.0 Hz), 136.4, 134.8, 134.6, 131.6, 131.4, 127.0, 126.5, (q, J = Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 11 H 6 F 3 O 2 [M+H] + : , found O CF 3 N Ph Ph (3m) Yellow solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ 8.54 (d, J = 8.0 Hz, 1H), 7.48 (t, J = 7.5 Hz, 1H), 7.41 (t, J = 7.0 Hz, 1H), (m, 3H), (m, 3H), (m, 2H), (m, 2H), 6.71 (d, J = 8.5 Hz, 1H); 13 C-NMR (CDCl 3, 125 MHz) δ 174.6, 154.0, 141.8, 138.3, 133.2, 132.7, 130.1, 129.5, , , 128.7, 127.5, 126.5, 126.3, 124.9, (q, J = Hz), 118.4, (q, J = 27.5 Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 22 H 15 F 3 NO [M+H] + : , found (3n) Yellow solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.83 (d, J = 8.5 Hz, 2H), 7.37 (s, 1H), (m, 4H), 6.82 (d, J = 9.0 Hz, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 191.0, 161.2, 136.2, (q, J = 5.8 Hz), 132.5, 130.7, 130.4, 129.0, (q, J = 24.0 Hz), 128.2, (q, J = Hz), 115.9; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 11 ClF 3 O 2 [M+H] + : , found S5

6 (5a) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 1H), (m, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 161.7, 149.9, (q, J = 5.6 Hz), 132.1, 130.6, 129.5, 129.3, 128.7, 128.3, 126.3, (q, J = 31.5 Hz), (q, J = Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 12 F 3 O 2 [M+H] + : , found (5b) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.76 (s, 1H), (m, 2H), 7.62 (s, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.37 (t, J = 7.5 Hz, 2H), (m, 1H), 7.02 (d, J = 8.0 Hz, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 161.0, 149.7, (q, J = 5.6 Hz), 132.9, 132.2, (q, J = 32.0 Hz), 129.6, 129.3, (q, J = 3.6 Hz), 126.5, (q, J = 3.6 Hz), (q, J = Hz), (q, J = Hz), 120.9; 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F), (s, 3F); HRMS (ESI) m/z calculated for C 17 H 11 F 6 O 2 [M+H] + : , found (5c) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.53 (s, 1H), (m, 2H), (m, 4H), (m, 1H), (m, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 161.4, 149.8, (q, J = 5.6 Hz), 136.8, 130.7, 130.4, 129.6, , , 126.5, (q, J = 32.0 Hz), (q, J = Hz), 121.0; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 11 ClF 3 O 2 [M+H] + : , found (5d) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ 7.52 (s, 1H), 7.42 (d, J = 8.0 Hz, 2H), 7.37 (t, J = 7.5 Hz, 2H), (m, 3H), 7.07 (d, J = 8.0 Hz, 2H), 2.37 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 161.9, 149.9, (q, J = 5.5 Hz), 141.3, 129.6, 129.5, 129.4, 129.0, 126.3, 123.3, 121.7, 121.5, 121.1, 21.4; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 17 H 14 F 3 O 2 [M+H] + : , found (5e) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 1H), (m, 3H), (m, 3H), (m, 2H), 5.22 (s, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 163.1, (q, J = 5.6 Hz), 134.3, 132.0, 130.2, 129.0, S6

7 128.6, , , 128.4, 128.2, 128.1, 123.4, (q, J = Hz); 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 17 H 13 F 3 NaO 2 [M+Na] + : , found (5f) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 8H), 7.25 (d, J = 8.5 Hz, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 188.9, (q, J = 5.6 Hz), 136.5, 136.1, 135.5, 131.6, 130.8, 129.7, 128.7, 124.6, (q, J = Hz); 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 11 ClF 3 OS [M+H] + : , found (5g) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 5H), (m, 1H), 3.01 (s, 3H), 2.77 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 164.0, (q, J = 5.7 Hz), 132.2, 130.2, 128.9, 128.7, (q, J = 30.0 Hz), (q, J = Hz), 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 12 H 13 F 3 NO [M+H] + : , found (5h) Yellow liquid; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 7.08 (s, 1H), (m, 1H), (m, 1H), 1.48 (d, J = 7.0 Hz, 6H), 1.08 (d, J = 6.5 Hz, 3H), 0.48 (d, J = 6.5 Hz, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 162.6, (q, J = 5.7 Hz), 132.7, 129.9, 129.5, 129.1, 128.5, (q, J = 30.0 Hz), (q, J = Hz), 51.1, 46.1, 20.3, 20.1, 19.8, 19.1; 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 21 F 3 NO [M+H] + : , found Cl O F 3 C N H Ph (5i) White solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 3H), (m, 3H), (m, 3H), (m, 1H); 13 C-NMR (CDCl 3, 125 MHz) δ 161.0, (q, J = 5.6 Hz), 135.2, 131.4, 130.7, 130.4, 130.0, 129.2, 129.1, 129.0, 128.3, (q, J = 30.0 Hz), (q, J = Hz), 121.5; 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 12 ClF 3 NO [M+H] + : , found S7

8 (5j) White solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 3H), (m, 5H), 7.19 (s, 1H), (m, 2H), 6.12 (s, 1H), 4.43 (d, J = 6.0 Hz, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 162.8, 136.6, (q, J = 5.8 Hz), 131.7, 130.1, 129.1, 128.7, 128.6, 127.9, 127.6, (q, J = 30.0 Hz), (q, J = Hz), 43.8; 9 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 17 H 15 F 3 NO [M+H] + : , found (5k) White solid, m.p o C; 1 H-NMR (500 MHz, DMSO) δ 8.12 (s, 1H), 7.80 (s, 1H), (m, 2H), (m, 3H), (m, 1H); 13 C-NMR (125 MHz, DMSO) δ 158.9, (q, J = 5.6 Hz), 126.8, 124.5, 123.7, 123.2, (q, J = 29.5 Hz), (q, J = Hz); 9 F-NMR (470.2 MHz, DMSO) δ (s, 3F); HRMS (ESI) m/z calculated for C 10 H 9 F 3 NO [M+H] + : , found (7a) White solid, m.p o C; 1 H-NMR (500 MHz, DMSO) δ 7.6 (d, J = 16.0 Hz, 1H), (m, 2H), (m, 2H), (m, 3H), (m, 3H), (m, 1H), 6.27 (d, J = 16.0 Hz, 1H), (m, 1H), 4.24 (t, J = 5.0 Hz, 2H), (m, 2H); 13 C-NMR (DMSO, 125 MHz) δ 166.7, 163.2, 145.5, (q, J = 5.5 Hz), 134.0, 131.8, 130.5, 130.4, 129.0, 128.9, 128.8, 128.0, (d, J = 29.6 Hz), (q, J = Hz), 117.0, 62.4, 39.1; 9 F-NMR (470.2 MHz, DMSO) δ (s, 3F); HRMS (ESI) m/z calculated for C 21 H 19 F 3 NO 3 [M+H] + : , found (7b) Yellow liquid; 1 H-NMR (500 MHz, DMSO) δ 7.71 (d, J = 7.5 Hz, 1H), 7.64 (s, 1H), 7.54 (s, 1H), 7.49 (s, 1H), (m, 5H), 7.34 (t, J = 7.5 Hz, 1H), (m, 6H); 13 C-NMR (CDCl 3, 125 MHz) δ 191.3, 161.1, 150.1, (q, J = 5.5 Hz), (q, J = 5.7 Hz), 136.8, 131.9, 131.6, 130.7, 130.3, 129.8, 129.4, 129.2, , , 127.6, 127.1, (q, J = Hz), (q, J = 272 Hz), 121.7; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F), (s, 3F); HRMS (ESI) m/z calculated for C 26 H 17 F 6 O 3 [M+H] + : , found S8

9 (Trifluridine) White solid, m.p o C; 1 H-NMR (500 MHz, DMSO) δ 11.8 (s, 1H), 8.73 (s, 1H), 6.08 (t, J = 6.0 Hz, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 2H), (m, 2H); 13 C-NMR (DMSO, 125 MHz) δ 159.6, 150.1, , , (q, J = Hz), (q, J = 6.6 Hz), 88.1, 85.9, 69.8, 60.7, 41.4; 19 F-NMR (470.2 MHz, DMSO) δ (s, 3F); HRMS (ESI) m/z calculated for C 10 H 11 F 3 N 2 NaO 5 [M+Na] + : , found (TF-Hymecromone) White solid, m.p o C; 1 H-NMR (500 MHz, DMSO) δ 11.0 (s, 1H), 7.85 (d, J = 9.0 Hz, 1H), 6.85 (d, J = 9.0 Hz, 1H), 6.69 (s, 1H), 2.56 (s, 3H); 13 C-NMR (DMSO, 125 MHz) δ 163.9, 157.0, 156.3, 155.2, 129.2, (q, J = Hz), 114.4, 111.4, (q, J = 29.2 Hz), 102.3, 15.9 (q, J = 3.7 Hz); 9 F-NMR (470.2 MHz, DMSO) δ (s, 3F); HRMS (ESI) m/z calculated for C 11 H 8 F 3 O 3 [M+H] + : , found (TF-Flavone) White solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ 8.27 (dd, J = 1.5, 8.0 Hz, 1H), (m, 1H), (m, 3H), (m, 2H), (m, 2H); 13 C-NMR (CDCl 3, 125 MHz) δ 174.3, , , 155.4, 134.7, 132.3, 131.3, (q, J = 1.5 Hz), 128.3, 126.1, 126.0, 123.6, 123.2, (q, J = Hz), 117.9, (q, J = 30.0 Hz); 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 16 H 10 F 3 O 2 [M+H] + : , found (TF-Tranilast) White solid, m.p o C; 1 H-NMR (500 MHz, CDCl 3 ) δ 11.0 (s, 1H), 8.83 (d, J = 8.5 Hz, 1H), 8.09 (d, J = 7.5 Hz, 1H), 7.66 (t, J = 8.0 Hz, 1H), 7.30 (s, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.05 (d, J = 8.5 Hz, 1H), 6.99 (s, 1H), 6.77 (d, J = 8.5 Hz, 1H), 3.80 (s, 3H), 3.59 (s, 3H); 13 C-NMR (CDCl 3, 125 MHz) δ 171.9, 162.2, 148.8, 140.9, (q, J = 5.6 Hz), 135.9, S9

10 135.8, 131.9, 124.3, 123.8, (q, J = Hz), 120.7, 114.4, 111.2, 110.7, 55.7, 55.5; 19 F-NMR (470.2 MHz, CDCl 3 ) δ (s, 3F); HRMS (ESI) m/z calculated for C 19 H 16 F 3 NNaO 5 [M+Na] + : found (2k-d) Yellow solid, 1 H-NMR (500 MHz, CDCl 3 ) δ (m, 2H), 7.50 (s, 1H), 7.40 (t, J = 8.0 Hz, 3H). S10

11 III. Crystallography Single-crystal X-ray diffraction data for the reported complex was recorded at a temperature of 293(2) K on a Oxford Diffraction Gemini R Ultra diffractometer, using a ω scan technique with Mo-Kα radiation (λ = Å). The structure was solved by Direct Method of SHELXS-97 and refined by full-matrix least-squares techniques using the SHELXL-97 program. 1 Non-hydrogen atoms were refined with anisotropic temperature parameters, and hydrogen atoms of the ligands were refined as rigid groups. Basic information pertaining to crystal parameters and structure refinement is summarized in Table (a) G. M. Sheldrick, SHELXS-97, Program for Solution of Crystal Structures, University of Göttingen, Germany, 1997; (b) G. M. Sheldrick, SHELXL-97, Program for Refinement of Crystal Structures, University of Göttingen, Germany, OH F 3 C O Cl 3n Table 1. Crystal data and structure refinement (CCDC ). Empirical formula C 16 H 10 ClF 3 O 2 Formula weight Temperature 293(2) K Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = (10) Å b = (2) Å c = (13) Å alpha = (5) deg. beta = (5) deg. gamma =90.000(5) deg. Volume (3) Å 3 Z 4 Calculated density Mg/m 3 Absorption coefficient mm -1 S11

12 F(000) Crystal size 0.21 x 0.18 x 0.14mm Theta range for data collection 2.31 to deg. Reflections collected / unique 7769 / 2899 [R(int) = ] Data / restraints / parameters 2899 / 0 / 199 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 =0.1198, wr2 = Table 2. Crystal data and structure refinement (CCDC ). Empirical formula C 10 H 8 F 3 NO Formula weight Temperature 293(2) K Crystal system Trigonal Space group R-3 Unit cell dimensions a = (18) Å b = 8.215(4) Å c = (9) Å alpha = 89.92(3) deg. beta = 89.79(3) deg. gamma = 84.28(4) deg. Volume 989.2(7) Å 3 Z 16 Calculated density Mg/m 3 Absorption coefficient mm -1 F(000) 496 Crystal size 0.21 x 0.18 x 0.14mm Theta range for data collection 2.89 to deg. Reflections collected / unique / 5172 [R(int) = ] Data / restraints / parameters 2684 / 7 / 121 S12

13 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 =0.1365, wr2 = R indices (all data) R1 = , wr2 = Table 3. Crystal data and structure refinement (CCDC ). Empirical formula C 19 H 16 F 3 NO 5 Formula weight Temperature 293(2) K Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = (12) Å b = (7) Å c = (12) Å alpha = (5) deg. beta = (2)deg. gamma =90.000(5) deg. Volume (3) Å 3 Z 4 Calculated density Mg/m 3 Absorption coefficient mm -1 F(000) Crystal size 0.21 x 0.18 x 0.14mm Theta range for data collection 2.73 to deg. Reflections collected / unique 9584 / 3616 [R(int) = ] Data / restraints / parameters 3616 / 0 / 253 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = S13

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