Supporting Information

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1 Supporting Information Metal-Free Direct Intramolecular Carbotrifluoromethylation of Alkenes to Functionalized Trifluoromethyl Azaheterocycles Lei Li, Min Deng, Sheng-Cai Zheng, Ya-Ping Xiong, Li-Jiao Zhao, Bin Tan,* and Xin-Yuan Liu* Department of Chemistry, South University of Science and Technology of China, Shenzhen, , P. R. China Table of Contents General information.s2 Experiments for mechanism study. S3 Synthesis of starting materials. S7 Synthesis of oxindoles (2a-2l).S7 Synthesis of isoquinolinediones (4a-4e) S11 Synthesis of oxindoles (6a-6h)...S13 Table S S17 References..S18 Spectra...S19 S1

2 General information. All reactions were carried out under argon using Schlenk techniques. Reagents were purchased at the commercial quality and used without further purification, KF was activated by muffle furnace in high temperature. Analytical thin layer chromatography (TLC) was performed on precoated silica gel 60 GF254 plates. Flash column chromatography was performed using Tsingdao silica gel (60, particle size mm). Visualization on TLC was achieved by use of UV light (254 nm) or iodine. NMR spectra were recorded on a Bruker DPX 400 spectrometer at 400 MHz for 1 H NMR, 100 MHz for 13 C NMR and 376 MHz for 19 F NMR in CDCl 3 with tetramethylsilane (TMS) as internal standard. The chemical shifts are expressed in ppm and coupling constants are given in Hz. Data for 1 H NMR are recorded as follows: chemical shift (ppm), multiplicity (s, singlet; d, doublet; t, triplet; q, quarter; m, multiplet), coupling constant (Hz), integration. Data for 13 C NMR are reported in terms of chemical shift (δ, ppm). 19 F NMR spectra were recorded on a Bruker DPX 400 MHz spectrometer (CFCl 3 as an external reference (0 ppm)). Mass spectrometric data were obtained using Bruker Apex IV RTMS. S2

3 Experiments for mechanism study 1 1. Reaction of TEMPO with PhI(OAc) 2 and Me 3 SiCF 3 Under argon, a 25 ml Schlenk tube equipped with a magnetic stir bar was charged with activated KF (1.6 mmol, 93.0 mg, 4.0 equiv.), EtOAc (super dry, 4.0 ml), trimethyl(trifluoromethyl)silane (1.6 mmol, l, 4.0 equiv.), 2,2,6,6-tetramethyl -1-piperidinyloxy (TEMPO, 0.8 mmol, mg, 2.0 equiv.) and Iodobenzene diacetate (0.8 mmol, mg, 2.0 equiv.). The sealed tube was stirred at 50 C for 2 h, then cooled to room temperature, α,α,α-trifluorotoluene (internal standard, 58.4 mg, 0.4 mmol) was added. 19 F NMR analysis of this reaction mixture showed that TEMPO-CF 3 was formed in 27% yield, then the reaction mixture was stirred another for 3 h at 50 C, 19 F NMR showed that TEMPO-CF 3 was formed in 65% yield. S3

4 2. Reaction of TEMPO and PhI(OAc) 2 and Me 3 SiCF 3 with N-methyl-Nphenylmethacrylamide (1a) Under argon, a 25 ml Schlenk tube equipped with a magnetic stir bar was charged with activated KF (1.6 mmol, 93.0 mg, 4.0 equiv.), 1a (0.4 mmol, 70.0 mg, 1.0 equiv.), EtOAc (super dry, 4.0 ml), trimethyl(trifluoromethyl)silane (1.6 mmol, l, 4.0 equiv.), 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO, mg, 0.8 mmol, 2.0 equiv.) and Iodobenzene diacetate (0.8 mmol, mg, 2.0 equiv.). The sealed tube was stirred at 50 C for 2 h, then cooled to room temperature, α,α,α-trifluorotoluene (internal standard, 58.4 mg, 0.4 mmol) was added. 19 F NMR analysis of this reaction mixture showed that TEMPO-CF 3 was formed in 45% yield and no any product (2a), then the reaction mixture was stirred for another 3 h at 50 C, 19 F NMR showed that TEMPO-CF 3 was formed in 90% yield and the product (2a) was not detected. S4

5 S5

6 3. Reaction of 2,6-di-tert-butyl-4-methylphenol (BHT) and PhI(OAc) 2 and Me 3 SiCF 3 with N-methyl-N-phenylmethacrylamide (1a) Under argon, a 25 ml Schlenk tube equipped with a magnetic stir bar was charged with activated KF (1.6 mmol, 93.0 mg, 4.0 equiv.), 1a (0.4 mmol, 70.0 mg, 1.0 equiv), EtOAc (super dry, 4.0 ml), trimethyl(trifluoromethyl)silane (1.6 mmol, l, 4.0 equiv.), 2,6-di-tert-butyl-4-methylphenol (BHT, 0.8 mmol, mg, 2.0 equiv) and Iodobenzene diacetate (0.8 mmol, mg, 2.0 equiv.).the sealed tube was stirred at 50 C for 15 h, then cooled to room temperature, α,α,α-trifluorotoluene (internal standard, 58.4 mg, 0.4 mmol) was added. 19 F NMR analysis of this reaction mixture showed that the product (2a) was not detected. S6

7 Synthesis of starting materials All starting materials were prepared according to the literature: 1a-1l 2, 3a-3e 3, 5a-5h 4. Synthesis of oxindoles (2a-2l) Under argon, a 25 ml Schlenk tube equipped with a magnetic stir bar were charged with activated KF (1.6 mmol, 93.0 mg, 4.0 equiv.), N-aralacrylamide (0.4 mmol, 1.0 equiv.), EtOAc (super dry, 4.0 ml), trimethyl(trifluoromethyl)silane (1.6 mmol, l, 4.0 equiv.) and Iodobenzene diacetate (0.8 mmol, mg, 2.0 equiv.). The sealed tube was then stirred at 50 C for hours. After reaction completion (monitored by TLC), the mixture was then diluted with water (10 ml) and extracted with EtOAc (5 ml X 3), the organic layers were dried with anhydrous sodium sulfate, filtered and concentrated in vacuo, and the residue was purified by silica gel column chromatography (petroleum ether/etoac) to give the desired products. 1, 3-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2a (6a)) 4 1 H NMR (400 MHz, CDCl 3 ) δ 7.31 (dt, J = 8.0, 1.2 Hz, 1 H), 7.27 (d, J = 7.6 Hz, 1 H), 7.09 (dt, J = 8.0, 0.9 Hz, 1 H), 6.88 (d, J = 7.6 Hz, 1 H), 3.23 (s, 3 H), 2.83 (dq, J = 15.2, 10.8 Hz, 1 H), 2.65 (dq, J = 15.2, 10.8 Hz, 1 H), 1.41 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ , 142.8, 130.9, 128.4, (q, J CF = Hz), (d, J CF = 1.0 Hz), , , (d, J CF = 2.0 Hz), 40.5 (q, J CF = 2.0 Hz), 26.3, F NMR (376 MHz, CDCl 3 ) δ (t, J = 8.5 Hz). 1, 3, 5-trimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2b) 4 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1 H), 7.08 (s, 1 H), 6.77 (d, J = 8.0 Hz, 1H), 3.21 (s, 3 H), 2.80 (dq, J = 15.2, 10.8 Hz, 1 H), 2.63 (dq, J = 15.2, 10.8 Hz, 1 H), 2.35 (s, 3 H), 1.39 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.4, 140.4, 132.2, 131.0, 128.7, (q, J CF = Hz), 124.3, 108.1, 44.4 (d, J CF = 3.0 Hz), 40.5 (q, J CF = 28.0 Hz), 26.4, 25.0, S7

8 19 F NMR (376 MHz, CDCl 3 ) δ (s). 5-methoxy-1, 3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one (2c) 4 1 H NMR (400 MHz, CDCl 3 )δ 6.87 (d, J = 2.0 Hz, 1 H), 6.83 (dd, J = 8.4, 2.4 Hz, 1 H),, 6.78 (d, J = 8.4 Hz, 1H), 3.80 (s, 3 H), 3.21 (s, 3 H), 2.81 (dq, J = 15.2, 10.8 Hz, 1 H), 2.62 (dq, J = 15.2, 10.5 Hz, 1 H), 1.39 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.0, 155.9, 136.3, 132.3, (q, J CF = Hz), 112.5, (d, J CF = 1.6 Hz), 108.6, 55.7, 44.6 (d, J CF = 2.0 Hz), 40.5 (q, J CF = 28.0 Hz), 26.4, F NMR (376 MHz, CDCl 3 ) δ (s). 1, 3-dimethyl-5-nitro-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2d) 4 1 H NMR (400 MHz, CDCl 3 ) δ 8.30 (dd, J = 8.8, 2.4 Hz, 1 H), 8.17 (d, J = 2 Hz, 1 H),, 6.98 (d, J = 8.8 Hz, 1 H), 3.31 (s, 3 H), 3.21 (s, 3 H), 2.91 (dq, J = 15.2, 10.4 Hz, 1 H), 2.74 (dq, J = 15.2, 10.4 Hz, 1 H), 1.47 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.5, 148.5, 143.5, 131.7, 129.9, (q, J CF = Hz), 119.5, 108.2, 44.3 (d, J CF = 2.2 Hz), 40.5 (q, J CF = 28.4 Hz), 26.9, F NMR (376 MHz, CDCl 3 ) δ (s). 1, 3-dimethyl-7-phenyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2e) 4 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3 H), (m, 2 H), 7.26 (dd, J = 7.6, 1.6 Hz, 1H), 7.14 (dd, J = 7.6, 1.6 Hz, 1H), 7.09 (t, J = 7.6 Hz, 1H), 2.87 (dq, J = 15.2, 10.8 Hz, 1H), 2.75 (s, 3H), 2.68 (dq, J = 15.2, 10.4 Hz, 1H), 1.45 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ , 139.8, 138.8, 131.9, 131.5, 130.0, 127.9, 127.7, 125.9, (q, J CF = Hz), 122.5, , 43.7 (d, J CF = 2.2 Hz), 41.0 (q, J CF = 28.0 Hz), 30.5, S8

9 19 F NMR (376 MHz, CDCl 3 ) δ (t, J = 10.5 Hz). 5-fluoro-1, 3-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2f) 4 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2 H), 6.80 (dd, J = 9.2, 4.0 Hz, 1 H), 3.22 (s, 3 H), 2.82 (dq, J = 15.2, 10.8 Hz, 1 H), 2.62 (dq, J = 15.2, 10.4 Hz, 1 H), 1.40 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.1, 160.5, 158.1, 138.8, (d, J CF = 7.9 Hz), (q, J CF = Hz), , (d, J CF = 23.4 Hz), (d, J CF = 26.2 Hz), (d, J CF = 8.2 Hz), 44.8, 44.5 (q, J CF = 14.2 Hz), 26.6, F NMR (376 MHz, CDCl 3 ) δ (t, J = 8.2 Hz), (ddd, J =14.9, 10.7, 4.1 Hz). 5-bromo-1,3-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2g) 4 1 H NMR (400 MHz, CDCl 3 ) δ 7.44 (dd, J = 8.4, 2.0 Hz, 1 H), 7.38 (d, J = 2.0 Hz, 1 H), 6.77 (d, J = 8.4 Hz, 1 H), 3.22 (s, 3 H), 2.83 (dq, J = 15.2, 10.6 Hz, 1 H), 2.63 (dq, J = 15.2, 10.4 Hz, 1 H), 1.40 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 177.8, 160.5, 141.9, 133.0, 131.4, 126.8, (q, J CF = Hz), 115.3, 110.0, 44.5, 40.6 (q, J CF = 28.0 Hz), 26.5, F NMR (376 MHz, CDCl 3 ) δ (s). 1, 3, 4, 6-tetramethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2h) 4 1 H NMR (400 MHz, CDCl 3 ) δ 6.67 (s, 1 H), 6.55 (s, 1 H), 3.20 (s, 3 H), (m, 2 H), 2.34 (s, 3 H), 2.33 (s, 3 H), 1.42 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.9, 143.2, 138.4, 134.5, 126.6, 124.9, (q, J CF = Hz), 107.2, 44.7 (d, J CF = 2.3 Hz), 39.7 (q, J CF = 27.8 Hz), 26.5, 23.3, 21.6, S9

10 19 F NMR (376 MHz, CDCl 3 ) δ (t, J = Hz). 1-benzyl-3-methyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (2i) 4 1 H NMR (400 MHz, CDCl 3 ) δ (m, 6 H), 7.17 (td, J = 7.6, 1.2 Hz, 1 H), 7.04 (td, J = 7.6, 0.9 Hz, 1 H), 6.75 (d, J = 7.6 Hz, 1 H), 4.97 (d, J = 15.6 Hz, 1 H), 4.88 (d, J = 15.6 Hz, 1 H), 2.90 (dq, J = 15.2, 10.8 Hz, 1 H), 2.70 (dq, J = 15.2, 10.8 Hz, 1 H), 1.45 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.6, 141.8, 135.6, 130.9, 128.7, 128.4, 127.6, 127.2, (q, J CF = Hz), 123.5, 122.7, 109.6, 44.4, (q, J CF = 28.4 Hz), 40.0, F NMR (376 MHz, CDCl 3 ) δ (s). 3-methyl-1-phenyl-3-(2,2,2-trifluoroethyl)indolin-2-one (2j) 4 1 H NMR (400 MHz, CDCl 3 ) δ 7.54 (t, J = 8.0 Hz, 2 H), (m, 3 H), 7.33 (d, J = 7.6 Hz, 1 H), (m, 1 H), 7.13 (td, J = 7.6, 0.8 Hz, 1 H), 6.85 (d, J = 8.0 Hz, 1 H), 2.98 (dq, J = 15.2, 10.8 Hz, 1 H), 2.74 (dq, J = 15.2, 10.8 Hz, 1 H), 1.54 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 178.0, 142.9, 134.3, 130.7, 129.7, 128.5, 128.3, 126.6, (q, J CF = Hz), 123.8, 123.1, 109.8, (d, J CF = 2.0 Hz), 40.1 (q, J CF = 28.0 Hz), F NMR (376 MHz, CDCl 3 ) δ (s). 1-methyl-1-(2, 2, 2-trifluoroethyl)-5, 6-dihydro-1H-pyrrolo[3, 2, 1-iJ]quinolin- 2(4H)-one (2k) 4 1 H NMR (400 MHz, CDCl 3 ) δ 7.10 (d, J = 7.6 Hz, 1 H), 7.05 (d, J = 7.6 Hz, 1 H), S10

11 6.97 (t, J = 7.6 Hz, 1 H), 3.72 (t, J = 6.0 Hz, 2 H), (m, 3 H), 2.64 (dq, J = 15.2, 10.8 Hz, 1 H), (m, 2 H), 1.41 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 177.3, 138.5, 129.6, 127.2, (q, J CF = Hz), 122.0, (d, J CF = 1.5 Hz), 120.5, (d, J CF = 2.0 Hz), 40.4 (q, J CF = 28.0 Hz), 39.0, 24.52, 24.49, F NMR (376 MHz, CDCl 3 ) δ (s). (1-methyl-2-oxo-3-(2, 2, 2-trifluoroethyl)indolin-3-yl)methyl acetate (2l) 4 1 H NMR (400 MHz, CDCl 3 ) δ 7.37 (td, J = 7.6, 1.2 Hz, 1 H), 7.31 (d, J = 7.4 Hz, 1 H), 7.11 (td, J = 7.6, 0.8 Hz, 1 H), 6.92 (d, J = 7.8 Hz, 1 H), 4.41 (d, J = 10.8 Hz, 1 H), 4.09 (d, J = 10.8 Hz, 1 H), 3.26 (s, 3 H), (m, 2 H), 1.99 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 175.2, 170.1, 143.6, 129.3, 126.5, (q, J CF = Hz), 124.7, 122.7, 108.6, 67.0, (d, J CF = 2.0 Hz), 36.7 (q, J CF = 28.8 Hz), 26.5, F NMR (376 MHz, CDCl 3 ) δ (t, J = 10.3 Hz). Synthesis of isoquinolinediones (4a-4e) Under argon, a 50 ml Schlenk tube equipped with a magnetic stir bar were charged with activated KF (232.5 mg, 4.0 mmol, 4.0 equiv.), benzamides (1.0 mmol, 1.0 equiv) EtOAc (super dry, 10.0 ml), trimethyl(trifluoromethyl)silane (4.0 mmol, l, 4.0 equiv.), iodobenzene diacetate (2.0 mmol, 642 mg, 2.0 equiv.) and Na 2 CO 3 (2.0 mmol, mg, 2.0 equiv.). The sealed tube was then stirred at 50 C for hours. After reaction completion (monitored by TLC), the mixture was then diluted with water (10 ml) and extracted with EtOAc (10 ml X 3), the organic layers were dried with anhydrous sodium sulfate, filtered and concentrated in vacuo, and the residue was purified by silica gel column chromatography (petroleum ether/etoac) to give the desired products. 2, 4-dimethyl-6-phenyl-4-(2, 2, 2-trifluoroethyl)isoquinoline-1, 3(2H,4H)-dione (4a) S11

12 1 H NMR (400 MHz, CDCl 3 ) δ 8.33 (d, J = 8.0 Hz, 1 H), 7.68 (d, J = 1.6 Hz, 1 H), (m, 3 H), (m, 3 H), (m, 4 H), (m, 1 H), 1.70 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 174.7, 163.7, 146.9, 141.0, 139.7, 130.0, 129.2, 128.8, 127.5, 127.2, (q, J CF = Hz), 124.5, 123.1, 44.3 (q, J CF = 27.3 Hz), 43.9, 31.4, F NMR (376 MHz, CDCl 3 ) δ (s). HRMS (ESI) m/z calcd. for C 19 H 17 F 3 NO 2 [M+H] , found , 4, 6-trimethyl-4-(2, 2, 2-trifluoroethyl)isoquinoline-1,3(2H,4H)-dione(4b) 1 H NMR (400 MHz, CDCl 3 ) δ 8.16 (d, J = 8.0 Hz, 1 H), 7.28 (dd, J = 7.2, 0.8 Hz, 1 H), 7.21 (s, 1 H), 3.40 (s, 3 H), (m, 1 H), (m, 1 H), 2.46 (s, 3 H), 1.65 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 174.8, 163.9, 144.9, 140.5, 129.4, 129.3, 126.1, (q, J CF = Hz), 121.9, 44.4 (q, J CF = 27.5 Hz), (d, J CF = 2.0 Hz), 31.3, 27.4, F NMR (376 MHz, CDCl 3 ) δ (s). HRMS (ESI) m/z calcd. for C 14 H 15 F 3 NO 2 [M+H] , found chloro-2, 4-dimethyl-4-(2, 2, 2-trifluoroethyl)isoquinoline-1,3(2H,4H)-dione(4c) 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (d, J = 8.4 Hz, 1 H), (m, 2 H), 3.38 (s, 3 H), (m, 1 H), (m, 1 H), 1.63 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 174.0, 163.0, 142.2, 140.6, 131.0, 128.9, 126.0,125.0 (q, J CF = Hz), 122.9, 44.5 (q, J CF = 27.5), (d, J CF = 2.0 Hz), 31.0, F NMR (376 MHz, CDCl 3 ) δ (s). HRMS (ESI) m/z calcd. for C 13 H 11 ClF 3 NNaO 2 [M+Na] , found methoxy-2, 4-dimethyl-4-(2, 2, 2-trifluoroethyl)isoquinoline-1, 3(2H,4H)- dione(4d) S12

13 1 H NMR (400 MHz, CDCl 3 ) δ 8.24 (d, J = 8.8 Hz, 1 H), 7.00 (dd, J = 8.8, 2.4 Hz, 1 H), 6.87 (d, J = 2.4 Hz, 1 H), 3.90 (s, 3 H), (m, 4 H), (m, 1 H), 1.65 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 174.8, 164.1, 163.5, 142.7, 131.8, (q, J CF = 277.0), 117.4, 113.8, 111.3, 55.7, (d, J CF = 27.5 Hz), (d, J CF = 2.0 Hz), 31.4, F NMR (376 MHz, CDCl 3 ) δ (s). HRMS (ESI) m/z calcd. for C 14 H 15 F 3 NO 3 [M+H] , found , 4-dimethyl-4-(2, 2, 2-trifluoroethyl)isoquinoline-1, 3(2H,4H)-dione (4e) 1 H NMR (400 MHz, CDCl 3 ) δ 8.28 (td, J = 7.6, 1.2 Hz, 1 H), 7.66 (td, J = 7.6, 1.2 Hz, 1 H), 7.48 (td, J = 7.6, 1.2, Hz, 1 H), 7.42 (d, J = 8.0 Hz, 1 H), 3.41 (s, 3 H), 3.35 (dq, J = 14.8, 9.6 Hz, 1 H), 2.80 (dq, J = 14.8, 9.6 Hz, 1 H), 1.66 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 174.5, 163.7, 140.4, 133.8, 129.2, 128.0, 125.6, (q, J CF = 277.0), , 44.3 (q, J CF = 27.4 Hz), (d, J CF = 2.0 Hz), 31.1, F NMR (376 MHz, CDCl 3 ) δ (s). HRMS (ESI) m/z calcd. for C 13 H 13 F 3 NO 2 [M+H] , found Synthesis of oxindoles (6a-6g, 6h (2a)) Under argon, a 50 ml Schlenk tube equipped with a magnetic stir bar were charged with activated KF (232.5 mg, 4.0 mmol, 4.0 equiv.), N-tosylmethacrylamide (1.0 mmol, 1.0 equiv.) EtOAc (super dry, 10.0 ML), trimethyl(trifluoromethyl)silane (4.0 mmol, l, 4.0 equiv.) and Iodobenzene diacetate (2.0 mmol, mg, 2.0 equiv.). The sealed tube was then stirred at 70 C for hours. After reaction completion (monitored by TLC), the mixture was then diluted with water (10 ml) and extracted with EtOAc (10 ml X 3), the organic layers were dried with anhydrous sodium sulfate,filtered and concentrated in vacuo, and the residue was purified by S13

14 silica gel column chromatography (petroleum ether/etoac) to give the desired products. 1, 3-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6a (2a)) 4 1 H NMR (400 MHz, CDCl 3 ) δ 7.31 (dt, J = 8.0, 1.2 Hz, 1H), 7.27 (d, J = 7.6 Hz, 1H), 7.09 (dt, J = 8.0, 0.9 Hz, 1H), 6.88 (d, J = 7.6 Hz, 1H), 3.23 (s, 3H), 2.83 (dq, J = 15.2, 10.8 Hz, 1H), 2.65 (dq, J = 15.2, 10.8 Hz, 1H), 1.41 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ , 142.8, 130.9, 128.4, (q, J CF = Hz), (d, J CF = 1.0 Hz), , , (d, J CF = 2.0 Hz), 40.5 (q, J CF = 2.0 Hz), 26.3, F NMR (376 MHz, CDCl 3 ) δ (t, J = 8.4 Hz). 1, 3, 6-trimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6b) 5 1 H NMR (400 MHz, CDCl 3 ) δ 7.14 (d, J = 7.6 Hz, 1 H), 6.90 (dd, J = 7.6, 0.8 Hz, 1 H), 6.71 (s, 1 H), 3.21 (s, 3 H), (m, 1 H), (m, 1 H), 2.39 (s, 3 H), 1.38 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) 5 δ 178.8, 142.9, 138.7, 128.1, (q, J CF = Hz), 123.2, , 109.4, (d, J = 2.1 Hz), 40.7 (q, J CF = 28.0 Hz), 26.4, 25.0, F NMR (376 MHz, CDCl 3 ) δ (s). 6-(tert-butyl)-1, 3-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6c) 5 1 H NMR (400 MHz, CDCl 3 ) δ 7.17 (d, J = 8.0 Hz, 1 H), 7.08 (dd, J = 7.6, 1.6 Hz, 1 H), 6.86 (d, J = 1.6 Hz, 1 H), 3.24 (s, 3 H), (m, 2 H), 1.37 (s, 3 H), 1.33 (s, 9 H). 13 C NMR (101 MHz, CDCl3) δ 178.8, , 142.6, 128.0, (q, J CF = Hz), 123.0, 119.4, , (d, J CF = 2.0 Hz), 40.4 (q, J CF = 28.0 Hz), 34.9, 31.3, 26.2, S14

15 F NMR (376 MHz, CDCl 3 ) δ (s). 6-chloro-1, 3-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6d) 5 1 H NMR (400 MHz, CDCl 3 ) δ 7.16 (d, J = 8.0 Hz, 1 H), 7.05 (dd, J = 8.0, 2.0 Hz, 1 H), 6.87 (d, J = 2.0 Hz, 1 H), 3.20 (s, 3 H), (m, 1 H), (m, 1 H), 1.38 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) 5 δ 178.4, 144.0, 134.3, 129.3, (q, J CF = Hz), 124.5, 122.5, 109.3, 44.1, 40.5 (q, J CF = 28.2 Hz), 26.5, C NMR (100 MHz, CDCl 3 ) 5 δ 178.4, 144.0, 134.3, 129.3, (q, J CF = Hz), 124.5, 122.5, 109.3, 44.1, 40.5 (q, J CF = 28.2 Hz), 26.5, F NMR (376 MHz, CDCl 3 ) δ (s). 1-butyl-3, 6-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6e) 5 1 H NMR (400 MHz, CDCl 3 ) δ 7.13 (d, J = 7.2 Hz, 1 H), 6.88 (dd, J = 7.6, 0.4 Hz, 1 H), 6.70 (s, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), 2.39 (s, 3 H), (m, 2 H), (m, 5 H), 0.97 (t, J = 7.2 Hz, 3 H). 13 C NMR (101 MHz, CDCl3) δ 178.6, 142.3, 138.5, 128.1, (q, J CF = Hz) 123.3, 122.8, 109.5, (d, J CF = 2.0 Hz), 40.5 (q, J CF = 27.9 Hz), 39.8, 29.2, 25.3, 21.8, 20.0, F NMR (376 MHz, CDCl 3 ) δ (s). 1-isopropyl-3,6-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6f) 5 1H NMR (400 MHz, CDCl3) δ 7.12 (d, J = 8.0 Hz, 1H), (m, 2H), S15

16 (m, 1 H), (m, 1H), (m, 1H), 2.38 (s, 3H), 1.48 (d, J = 4.8 Hz, 3H), 1.46 (d, J = 4.8 Hz, 3H), 1.35 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 178.4, 141.6, 138.2, 128.3, (q, J CF = Hz), 123.4, 122.5, 110.9, 43.8, (d, J CF = 2.1 Hz), 40.6 (q, J CF = 27.8 Hz), 25.3, 21.9, 19.1, F NMR (376 MHz, CDCl 3 ) δ (s). 1-benzyl-3, 6-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one (6g) 5 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5 H), 7.18 (d, J = 7.6 Hz, 1 H), 6.90 (d, J = 7.6 Hz, 1 H), 6.62 (s, 1 H), 5.00 (d, J = 16 Hz, 1 H), 4.90 (d, J = 16 Hz, 1 H), (m, 1 H), (m, 1 H), 2.32 (s, 3 H), 1.47 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ) δ 179.0, 142.1, 138.6, 135.8, 128.8, 128.0, 127.6, 127.2, (q, J CF = Hz), , , 110.4, 44.2, 43.9, 40.5 (q, J CF = 28.0 Hz), 25.8, F NMR (376 MHz, CDCl 3 ) δ (s). 1-(4-chlorobenzyl)-3, 6-dimethyl-3-(2, 2, 2-trifluoroethyl)indolin-2-one (6h) 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), 7.14 (d, J = 7.6 Hz, 1H), (m, 1H), 6.55 (s, 1H), 4.95 (d, J = 8.8 Hz, 1H), 4.79 (d, J = 8.8 Hz, 1H), (m, 1H), (m, 1H), 2.30 (s, 3H), 1.43 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 179.1, 141.9, 138.8, 134.5, 133.6, 129.3, 129.1, 128.8, 128.1, (q, J CF = Hz), (d, J CF = 4.0 Hz), 110.3, 44.3 (d, J CF = 2.0 Hz), 43.40, 40.6 (q, J CF = 28.0 Hz), 25.9, C NMR (101 MHz, CDCl3) δ 178.9, 141.7, 138.6, 134.3, 133.4, 128.9, 128.5, 127.9, (q, J = Hz), , , 110.1, (d, J = 2.2 Hz), 43.2, 40.4 (q, J = 28.0 Hz), 25.8, F NMR (376 MHz, CDCl 3 ) δ (s). HRMS (ESI) m/z calcd. for C 19 H 18 ClF 3 NO [M+H] , found S16

17 Table S1. Screening results of reaction conditions. a Entry PhI(OR) 2 Additive Solvent T ( C) Yield (%) b 1 PhI(OAc) 2 KF 1,4-dioxane PhI(OAc) 2 KF DCE PhI(OAc) 2 KF THF PhI(OAc) 2 KF CHCl PhI(OAc) 2 KF CH 3 CN 50 N.R. 6 PhI(OAc) 2 KF EtOAc c 7 PhI(OAc) 2 KF EtOAc RT 53 8 PhI(OAc) 2 KF EtOAc PhI(OPiv) 2 KF EtOAc PhI(OCOCF 3 ) 2 KF 1,4-dioxane d PhI(OAc) 2 KF EtOAc PhI(OAc) 2 CsF EtOAc PhI(OAc) 2 Cs 2 CO 3 EtOAc a Reaction conditions: (Unless otherwise mentioned) 1a (0.4 mmol), TMSCF 3 (1.6 mmol), KF (1.6 mmol), PhI(OAc) 2 (0.8 mmol) in dry solvents. b Determined by 19 F NMR spectroscopy using PhCF 3 as an internal standard. c Isolated yield. d 4 Å MS (200 mg) was added. PhI(OPiv) 2 = Bis(tert-butylcarbonyloxy)iodobenzene S17

18 References: (1) (a) Xu, C.; Liu, J.; Ming, W.; Liu, Y.; Liu, J.; Wang, M.; Liu, Q. Chem. Eur. J. 2013, 19, (b) Wang, X.; Zhang, S.; Feng, J.; Xu, Y.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2011,133, (2) (a) Pinto, A.; Jia, Y.; Neuville, L.; Zhu, J. Chem. Eur. J. 2007, 13, 961. (b) Jones, K.; Thompson, M.; Wright, C. J. Chem. Soc., Chem. Commun. 1986, 715. (c) Wei, H.; Piou, T.; Dufour, J.; Neuville, L.; Zhu, J. Org. Lett. 2011, 13, (3) Sibi, M. P.; Prabagaran, N.; Ghorpade S. G.; Jasperse, C. P. J. Am. Chem. Soc. 2003, 125, (4) Fabry, D. C.; Stodulski, M.; Hoerner, S.; Gulder, T. Chem. Eur. J. 2012, 18, (5) Mu, X.; Wu, T.; Wang, H.; Guo, Y.-L.; Liu, G.-S. J. Am. Chem. Soc. 2012, 134, 878. (6) Kong, W.; Casimiro, M.; Merino, E.; Nevado, C. J. Am. Chem. Soc. 2013, 135, S18

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