Supporting Information. Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template

Supporting Information Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template Hua-Jin Xu, Yi Lu, *, Marcus E. Farmer, Huai-Wei Wang, Dan Zhao, Yan-Shang Kang, Wei-Yin Sun, *, Jin-Quan Yu *, Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, China. Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California 92037, USA. Table of Contents 1. General Information... S2 2. Experimental Section... S2 2.1 Preparation and characterization of substrates... S2 2.2 References... S12 2.3 Optimization Studies... S13 2.4 General procedure for Rh (III)-catalyzed meta-c-h Olefination... S20 2.5 meta-c H Olefination of Indoline and N-Methylaniline.S40 2.6 Kinetic Isotope Effect Studies..S40 2.7 The Procedure for the 10 mmol Reaction in Toluene..S43 3. NMR Spectra for New Compounds... S44 S1

1. General Information Anhydrous solvents were prepared according to standard methods. Commercially available chemicals were used as received without further purification. NMR spectra were recorded on 300 MHz, 400 MHz and 600 MHz spectrometers. Chemical shifts are quoted in ppm relative to CDCl 3. High-resolution mass spectra (HRMS) were obtained with a Q-TOF (ESI). 2. Experimental Section 2.1 Preparation and characterization of substrates 2.1.1 Procedure for the preparation of template (T 3 ) 1 Toa 100 ml round bottom flask was added 2-fluorobenzonitrile (20 mmol, 1.0 equiv), 2-fluoroaniline (20 mmol, 1.0 equiv) and t BuOK (42 mmol, 2.1 equiv). Next, 60 ml dry DMSO was added and the reaction wasstirred overnight at room temperature.the reaction was poured into ice waterand the resulting precipitate was filtered and washed with water to provide a crude solid. The crude productwaspurified either by column chromatography (EtOAc/hexanes = 1:4) or recrystallization from methanol. S2 2-(2-fluorophenylamino)benzonitrile (T 3 ): 1 H NMR (400 MHz, CDCl 3 ) δ 7.54 (dd, J = 8.0, 1.6 Hz, 1 H), 7.41 (td, J = 8.8, 1.6 Hz, 1 H), 7.34 (td, J = 8.0, 2.4 Hz, 1 H), 7.20-7.07 (m, 4 H), 6.91 (td, J = 7.6, 1.2 Hz, 1 H), 6.25 (br, 1 H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.31 (d, J C-F = 195.4 Hz), 146.54, 133.57 (d, J C-F = 83.5 Hz),

128.20 (d, J C-F = 9.5 Hz), 124.98 (d, J C-F = 5.9 Hz), 124.65 (d, J C-F = 2.7 Hz), 122.72, 120.111, 117.34, 116.47 (d, J C-F = 15.5 Hz), 114.78, 99.62; HRMS (EI-TOF): m/zcalcd. for C 13 H 10 FN 2 [M+H] + : 213.0823, found 213.0824. 2.1.2 General procedure for the preparation of substrates (1a-1). 2 To an ice cooled solution of template (T 3 ) (1.0 mmol, 1.0 equiv) in dry THF (10 ml) was added NaH (60% in mineral oil, 1.2 mmol, 1.2 equiv) in two portions at 0 o C andthe solution was stirred for another 1h at this temperature. Next, the acid chloride (1.0 mmol, 1.0 equiv.), prepared from the corresponding carboxylic acid and oxalyl chloride, was added dropwise to the reaction mixture at 0 o C. The reaction was stirred overnight, then quenched with water, and extracted with DCM three times.the combined organic extractsweredried over MgSO 4 and concentrated in vacuo. The crude product was purified by column chromatography (EtOAc/hexanes = 3:1) to yield the pure product in moderate yield. N-(2-cyanophenyl)-N- (2-fluorophenyl)-3-phenylpropanamide (1a): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (dd, J = 8.0, 1.6 Hz, 1 H), 7.59 (td, J = 7.6, 1.2 Hz, 1 H), 7.46-7.31 (m, 4 H), 7.28-7.13 (m, 7 H), 3.05 (t, J = 8.0 Hz, 2 H), 2.62 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.87, 158.25 (d, J C-F = 247.6 Hz), 144.80, 140.88, 133.85 (d, J C-F = 4.3 Hz), 130.82, 129.41, 128.99, 128.66, 128.59, 128.56, 127.92, 126.45, 126.31, 125.62, 117.31 (d, J C-F = 20.7 Hz), 117.01, 113.10, 36.15, 31.21; HRMS (EI-TOF): m/zcalcd. for C 22 H 18 FN 2 O [M+H] + : 345.1398, found 345.1401. S3

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-phenylbutanamide (1b): 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (s, 1 H), 7.54 (t, J = 6.8 Hz, 1 H), 7.36 (m, 2 H), 7.29-7.12 (m, 9 H), 3.49-3.43 (m, 1 H), 2.65-2.49 (m, 2 H), 1.36 (d, J = 6.4 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.34, 158.81 (d, J C-F = 245.3 Hz), 146.07, 144.64, 133.82 (d, J C-F = 38.8 Hz), 130.84, 129.46 (d, J C-F = 13.2 Hz), 129.08, 128.55, 127.85, 126.96, 126.39, 125.50, 124.79, 117.25 (d, J C-F = 20.5 Hz), 116.85, 112.97, 42.72, 36.36, 21.43; HRMS (EI-TOF): m/zcalcd. for C 23 H 20 FN 2 O [M+H] + : 359.1554, found 359.1552. N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-o-tolylpropanamide (1c): 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (dd, J = 7.8, 1.8 Hz, 1 H), 7.59 (td, J = 7.8, 1.8 Hz, 1 H), 7.48-7.33 (m, 4 H), 7.26-7.10 (m, 6 H), 3.05 (t, J = 7.8 Hz, 2 H), 2.57 (t, J = 7.8 Hz, 2 H), 2.20 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 173.00, 157.75 (d, J C-F = 249.1 Hz), 144.82, 138.94, 136.18, 133.82 (d, J C-F = 47.6 Hz), 130.76, 130.37, 129.47, 129.01, 127.91, 126.50, 126.23, 125.65, 117.32 (d, J C-F = 20.7 Hz), 117.00, 113.09, 34.76, 28.80, 19.16; HRMS (EI-TOF): m/zcalcd. for C 23 H 20 FN 2 O [M+H] + : 359.1554, found 359.1556. S4 N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(2-methoxyphenyl)propanamide (1d): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (dd, J = 8.0, 1.2 Hz, 1 H), 7.58 (td, J = 8.0,

1.6Hz, 1 H), 7.45-7.32 (m, 4 H), 7.18-7.14 (m, 4 H), 6.87 (t, J = 7.2 Hz, 1 H), 6.78 (d, J = 8.0 Hz, 1 H), 3.70 (s, 3 H), 3.05 (t, J = 7.6 Hz, 2 H), 26.3 (s, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 173.45, 158.25 (d, J C-F = 247.0 Hz), 157.58, 144.84, 133.76 (d, J C-F = 38.9 Hz), 130.90, 130.57, 130.38, 129.68, 129.02, 127.77, 127.64, 125.39, 120.51, 117.10 (d, J C-F = 24.0 Hz), 116.98, 113.03, 110.20, 55.05, 34.14, 26.66; HRMS (EI-TOF): m/zcalcd. for C 23 H 20 FN 2 O 2 [M+H] + : 375.1503, found 375.1504. N-(2-cyanophenyl)-N,3-bis(2-fluorophenyl)propanamide (1e): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.46 (d, J = 7.2 Hz, 1 H), 7.37-7.33 (m, 3 H), 7.23-7.14 (m, 4 H), 7.04 (t, J = 7.2 Hz, 1 H), 6.95 (td, J = 8.0, 1.2 Hz, 1 H), 3.07 (t, J = 7.6 Hz, 2 H), 2.62 (s, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.63, 161.22 (d, J C-F = 243.9 Hz), 158.22 (d, J C-F = 249.5 Hz),144.70, 133.81 (d, J C-F = 49.0 Hz), 130.92 (d, J C-F = 37.9 Hz), 130.89, 129.27, 128.93, 128.10 (d, J C-F = 7.7 Hz), 127.90, 127.55 (d, J C-F = 16.1 Hz), 125.63, 124.17 (d, J C-F = 3.4 Hz), 117.29 (d, J C-F = 20.1 Hz),116.98, 115.27 (d, J C-F = 21.7 Hz), 112.99, 34.39, 24.91; HRMS (EI-TOF): m/zcalcd. for C 22 H 17 F 2 N 2 O [M+H] + : 363.1303, found 363.1300. S5 3- (2-chlorophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1f): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 8.0 Hz, 1 H), 7.57 (t, J = 7.6 Hz, 1 H), 7.45 (t, J = 7.2 Hz, 1 H), 7.36-7.31 (m, 3 H), 7.28-7.25 (m, 2 H), 7.22-7.12 (m,4 H), 3.15 (t, J = 7.6 Hz, 2 H), 2.64 (s, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.63, 158.20 (d, J C-F = 248.1 Hz), 144.66, 138.24, 133.96, 133.77 (d, J C-F = 50.8 Hz), 130.96, 130.83, 130.73, 129.48, 129.28, 128.86, 127.87, 127.03, 125.60, 124.87,

117.26 (d, J C-F = 20.0 Hz), 116.95, 112.94, 33.92, 29.39; HRMS (EI-TOF): m/zcalcd. for C 22 H 17 ClFN 2 O [M+H] + : 379.1008, found 379.1005. 3-(2-bromophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1g): 1 H NMR (400MHz, CDCl 3 ) δ 7.72 (d, J = 7.6,Hz, 1 H), 7.58 (t, J = 7.8 Hz, 1 H), 7.47-7.26 (m, 6H), 7.23-7.19 (m, 3H), 7.05 (t, J = 7.2 Hz, 1 H), 3.15(t, J = 8.0 Hz, 2 H), 2.65 (s, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.56, 158.24 (d, J C-F = 248.5 Hz), 144.68, 139.97, 133.77 (d, J C-F = 49.2 Hz), 132.82, 130.99, 130.77, 128.88, 128.12, 127.87, 127.71, 125.64, 124.37, 117.29 (d, J C-F = 20.3 Hz), 116.95, 112.98, 34.06, 31.86; HRMS (EI-TOF): m/zcalcd. for C 22 H 16 BrFN 2 NaO [M+Na] + : 445.0322, found 445.0323. N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(2-(trifluoromethyl)phenyl)propanam ide (1h): 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (dd, J = 7.6, 1.2Hz, 1 H),7.61-7.56 (m, 2 H), 2.48-7.28 (m, 7 H), 7.22-7.16 (m, 2 H), 3.23 (t, J = 8.0Hz, 2 H), 2.62(t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.48, 158.15 (d, J C-F = 249.5 Hz), 144.67, 139.55, 133.76 (d, J C-F = 52.4 Hz), 132.15, 131.61, 131.00, 130.69, 129.25, 128.93, 128.77, 128.47, 126.73 (q, J C-F = 233 Hz ), 126.50,126.04 (q, J C-F = 5.7 Hz), 125.90, 123.18, 120.46, 117.31 (d, J C-F = 20.4 Hz), 117.02, 113.05, 36.00, 28.15; HRMS (EI-TOF): m/zcalcd. for C 23 H 17 F 4 N 2 O [M+H] + : 413.1272, found 413.1275. S6

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-m-tolylpropanamide (1i): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (dd, J = 7.6, 1.6 Hz, 1 H), 7.58 (td, J = 8.0, 1.6 Hz, 1 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.40-7.32 (m,3 H), 7.23-7.14 (m, 3 H), 7.01 (d, J = 7.2 Hz, 1 H), 6.96-6.93 (m,2 H), 3.02 (t, J = 8.0 Hz, 2 H), 2.62 (t, J = 7.6 Hz, 2 H), 2.31 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.91, 158.17 (d, J C-F = 249.0 Hz), 144.79, 140.78, 138.16, 133.84 (d, J C-F = 46.7 Hz), 130.80, 129.35, 128.96, 128.47, 127.88, 127.01, 125.50, 117.28 (d, J C-F = 20.9 Hz), 116.98, 113.05, 36.19, 31.13, 21.43; HRMS (EI-TOF): m/zcalcd. for C 23 H 19 FN 2 NaO [M+Na] + : 381.1374, found 381.1373. N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-methoxyphenyl)propanamide (1j): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.37-7.32 (m,3 H), 7.23-7.16 (m, 3 H), 6.72 (d, J = 7.6 Hz, 2 H), 6.68 (d, J = 2.0 Hz, 1 H), 3.77 (s, 3 H), 3.03 (t, J = 8.0 Hz, 2 H), 2.62 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.78, 159.77, 158.17 (d, J C-F = 248.5 Hz),144.78, 142.47, 133.82 (d, J C-F = 48.0 Hz), 130.80, 129.56, 128.95, 127.90, 125.60, 120.87, 117.32 (d, J C-F = 20.5 Hz), 117.00, 114.16, 113.05, 111.74, 55.26, 36.08, 31.28;HRMS (EI-TOF): m/zcalcd. for C 23 H 19 FN 2 NaO 2 [M+Na] + : 397.1323, found 397.1327. S7

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-fluorophenyl)propanamide (1k): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.59 (t, J = 7.8 Hz, 1 H), 7.46-7.38 (m,3 H), 7.32 (d, J = 8.0 Hz, 1 H) 7.24-7.18 (m, 3 H), 6.93 (d, J = 7.6 Hz, 1 H), 6.89-6.81 (m, 2 H), 3.04 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.51, 162.87 (d, J C-F = 244.1 Hz), 158.17 (d, J C-F = 246.1 Hz), 144.73, 143.39 (d, J C-F = 6.2 Hz), 133.84 (d, J C-F = 49.5 Hz), 131.00 (d, J C-F = 6.8 Hz), 130.76,130.02 (d, J C-F = 8.3 Hz), 129.33, 128.96, 127.99, 125.69, 124.27, 117.34 (d, J C-F = 20.7 Hz), 116.99, 115.40 (d, J C-F = 20.9 Hz), 113.20 (d, J C-F = 20.9 Hz), 35.70, 30.85; HRMS (EI-TOF): m/zcalcd. for C 22 H 17 F 2 N 2 O [M+H] + : 363.1303, found 363.1307. 3-(3-chlorophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1l): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.2 Hz, 1 H), 7.44-7.38 (m,3 H), 7.32 (t, J = 8.0 Hz, 1 H), 7.26-7.17 (m, 4 H), 7.10 (s, 1 H), 7.04 (d, J = 6.8 Hz, 1 H), 3.02 (t, J = 7.6 Hz, 2 H), 2.60 (t, J = 7.2 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.42, 158.11 (d, J C-F = 249.2 Hz), 144.65, 142.84, 134.21, 133.70 (d, J C-F = 53.3 Hz), 131.00 (d, J C-F = 7.0 Hz), 130.69, 129.85, 129.29, 128.89, 128.61, 127.96, 126.82, 126.49, 125.68, 117.34 (d, J C-F = 20.1 Hz), 116.97, 112.97, 35.66, 30.76; HRMS (EI-TOF): m/zcalcd. for C 22 H 17 ClFN 2 O [M+H] + : 379.1008, found 379.1002. S8

3-(3-bromophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1m): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.59 (t, J = 7.6 Hz, 1 H), 7.44-7.38 (m,3 H), 7.31 (t, J = 7.6 Hz, 1 H),7.26-7.08 (m, 6 H), 3.01 (t, J = 7.2 Hz, 2 H), 2.60 (t, J = 7.8 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.44, 158.11 (d, J C-F = 248.4Hz), 144.72, 143.20, 133.86 (d, J C-F = 50.4Hz), 131.57, 131.03, 130.75, 130.10, 129.48, 128.96, 127.98, 127.36, 125.72, 122.58, 117.37 (d, J C-F = 19.0 Hz), 116.97, 113.06, 35.73, 30.80; HRMS (EI-TOF): m/zcalcd. for C 22 H 16 BrFN 2 NaO [M+Na] + : 445.0322, found 445.0325. N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-(trifluoromethyl)phenyl)propanam ide (1n): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.58 (t, J = 7.2 Hz, 1 H), 7.45-7.36 (m,7 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.26-7.20 (m, 2 H), 3.11 (t, J = 7.2 Hz, 2 H), 2.65 (t, J = 7.2 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.30, 158.15 (d, J C-F = 249.1 Hz), 144.60, 141.66, 133.81 (d, J C-F = 55.9 Hz), 132.10, 131.21, 130.98, 130.69, 130.60 (d, J C-F = 4 Hz), 130.26, 129.02, 128.84, 127.97, 125.67, 125.15 (q, J C-F = 4.0 Hz), 123.17 (d, J C-F = 3.0 Hz), 122.88, 120.17, 117.32 (d, J C-F = 19.8 Hz), 116.95, 112.94, 35.58, 30.84; HRMS (EI-TOF): m/zcalcd. for C 23 H 16 F 4 N 2 NaO [M+Na] + : 435.1091, found 435.1095. S9

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(4-methoxyphenyl)propanamide (1o): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (dd, J = 7.6,1.2Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.37-7.32 (m,3 H), 7.20-7.18 (m, 2 H), 7.05 (d, J = 8.4 Hz, 2 H), 6.81 (d, J = 8.0 Hz, 2 H), 3.77 (s, 3 H), 3.00 (t, J = 8.0 Hz, 2 H), 2.59 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.62, 158.00 (d, J C-F = 248.8 Hz), 157.91, 144.47, 133.59 (d, J C-F = 58.5 Hz), 132.60, 130.72 (d, J C-F = 7.2 Hz), 130.50, 129.22, 129.12, 128.63, 127.68, 125.41, 124.65, 117.15 (d, J C-F = 20.0 Hz), 116.83, 113.75, 112.71, 55.07, 36.18, 30.09; HRMS (EI-TOF): m/zcalcd. for C 23 H 20 FN 2 O 2 [M+H] + : 375.1503, found 375.1503. N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(4-fluorophenyl)propanamide (1p): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.45 (t, J = 7.2 Hz, 1 H), 7.39-7.37 (m, 2 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.23-7.20 (m,2 H), 7.11-7.08 (m, 2 H), 6.93 (t, J = 8.0 Hz, 2 H), 3.02 (t, J = 7.6 Hz, 2 H), 2.60 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.62, 161.55 (d, J C-F = 242.4 Hz), 158.18 (d, J C-F = 248.5 Hz), 144.72, 136.46, 133.59 (d, J C-F = 51.0 Hz), 130.90,19.3 Hz), 117.00, 115.29 (d, J C-F = 21.0 Hz), 113.11, 36.10, 30.30; HRMS (EI-TOF): m/zcalcd. for C 22 H 16 F 2 N 2 NaO [M+Na] + : 385.1123, found 385.1124. N-(2-cyanophenyl)-N,3-diphenylpropanamide (1q): 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (dd, J = 7.6, 1.6 Hz, 2 H), 7.58 (t, J = 7.6Hz, 1 H),7.38-7.31 (m, 4 H), 7.31-7.18 (m, 6 H),7.13 (d, J = 7.2 Hz, 2 H), 3.04 (t, J = 7.6 Hz, 2 H), 2.64 (s, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.90, 145.47, 141.58, 140.90, 133.98, 133.63, S10

130.00, 129.09, 128.60, 128.52, 128.35, 127.65, 126.26, 117.06, 112.92, 36.57, 31.47; HRMS (EI-TOF): m/zcalcd. for C 22 H 18 N 2 O [M+H] + : 327.1497, found 327.1495. N-(2-cyanophenyl)-3-phenyl-N-o-tolylpropanamide (1r): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (dd, J = 7.6, 1.6 Hz, 1 H), 7.48 (t, J = 7.6Hz, 1 H),7.31-7.12 (m, 8 H), 7.12 (d, J = 7.6 Hz, 2 H), 7.03 (d, J = 7.6Hz, 1 H), 3.06 (t, J = 7.6 Hz, 2 H), 2.68-2.49 (m, 2 H), 2.23(s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.90, 144.08, 140.97, 140.31, 133.59, 133.42, 132.19, 129.72, 129.13, 128.58, 128.49, 128.34, 127.54, 127.05, 126.62, 126.20, 117.28, 112.45, 37.14, 31.34, 18.25; HRMS (EI-TOF): m/zcalcd. for C 23 H 21 N 2 O [M+H] + : 341.1654, found 341.1655. 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (dd, J = 7.6, 1.6 Hz, 1 H), 7.58 (td, J = 7.6, 1.6Hz, 1 H),7.46-7.31 (m, 4 H), 7.25-7.16 (m, 2 H), 3.05 (t, J = 7.6 Hz, 2 H), 2.62 (t, J = 7.6 Hz,2 H); 13 C NMR (100 MHz, CDCl 3 ) δ172.89, 158.23 (d, J C-F = 248.1 Hz), 144.76, 140.66, 133.82 (d, J C-F = 46.8 Hz), 130.80,129.50, 129.38, 128.97, 128.34,128.30, 128.05, 127.89, 127.81, 125.62, 117.30 (d, J C-F = 20.4 Hz), 116.99, 113.05, 36.12, 31.07; HRMS (EI-TOF): m/zcalcd. for C 22 H 13 D 5 FN 2 O [M+H] + : 350.1717, found 350.1716. S11

2.2 References (1) Gorvin, J. H. J. Chem. Soc., Perkin Trans. 1988, 1, 1331. (2) Wan, L.; Dastbaravardeh, N.; Li, G.; Yu, J.-Q. J. Am. Chem. Soc. 2013, 135, 18056. S12

2.3 Optimization Studies Table S1. Initial Screening Solvents a Table S2. Screening of Temperature a S13

S14 Table S3. Screening of Oxidants a

Table S4. Screening Equivalents of Oxidants a S15

Table S5. Screening of Additives a S16

Table S6.Screening of Time a S17

Table S7.Screening of Templates a S18

Table S8.Screening of theequivalentsof ethyl acrylate a S19

Table S9.Utilityof T 3 with Palladium catalysts a 2.4 General procedure for Rh (III)-catalyzed meta-c-h olefination To a 25 ml Schlenk-type sealed tube equipped with a magnetic stirring bar was added the substrate (0.1 mmol), [RhCp*Cl 2 ] 2 (3.1 mg, 0.005 mmol), Cu (CO 2 CF 3 ) 2 xh 2 O (28.9mg, 0.1 mmol), CF 3 CO 2 H (0.1 mmol), olefin (0.5 mmol) and DCE (2.0 ml). The tube was evacuated then back-filled with O 2 (3 times, balloon), capped, and heated to 100 C for 48 hours. After cooling to room temperature, the reaction mixture was filtered through a pad of silica gel. The silica gel was washed with an additional 10 ml of DCM. The filtrate was concentrated in vacuo to afford crude products, which was purified by flash column chromatography on silica gel using hexanes/etoac (3/1) as the eluent to give the pure product. S20

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)phenyl) acrylate (3a mono ): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.63 (d, J = 16.0 Hz, 1 H), 7.58 (td, J = 8.0, 1.6 Hz, 1 H), 7.44-7.35 (m, 4 H), 7.32-7.28(m, 3 H), 7.21-7.16(m, 3 H), 6.39 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H) 3.05(t, J = 7.6 Hz, 2 H), 2.62 (t, J = 7.2 Hz, 2 H), 1.34 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.59, 167.14, 158.21 (d, J C-F = 251.0 Hz), 144.62, 142.93, 141.57, 134.74, 133.86 (d, J C-F = 51.4 Hz), 130.95, 130.75, 130.61, 129.95, 129.16, 128.93, 128.28, 127.97,126.05, 125.67, 119.97, 118.39, 117.46 (d, J C-F = 19.7 Hz), 116.99, 113.02, 60.61, 35.87, 30.96, 14.44; HRMS (EI-TOF): m/zcalcd. for C 27 H 24 FN 2 O 3 [M+H] + : 443.1765, found 443.1766. (2E,2'E)-diethyl-3,3'-(5-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropy l)-1,3-phenylene)diacrylate (3a di ): 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (d, J = 7.2 Hz, 1 H), 7.63 (d, J = 16.0 Hz, 2 H), 7.58 (t, J = 8.0 Hz, 1 H), 7.51-7.38 (m, 4 H), 7.31-7.27 (m, 3 H), 7.22-7.20 (m, 2 H), 6.43 (d, J = 16.0 Hz, 2 H), 4.27 (q, J = 7.6 Hz, 2 H), 3.07 (t, J = 7.6 Hz, 2 H), 2.63 (s, 2 H), 1.35 (t, J = 7.2 Hz, 6 H); 13 C NMR (125 MHz, CDCl 3 ) δ 172.34, 166.87, 158.25 (d, J C-F = 166 Hz), 144.71, 143.75, 142.35, 135.497, 133.86 (d, J C-F = 52.2 Hz), 130.75, 130.61, 129.84, 128.92, 128.03, 125.69, 120.99, 119.97, 117.43 (d, J C-F = 13.1 Hz), 116.98, 113.06, 60.75, 35.67, S21

30.84, 14.44; HRMS (EI-TOF): m/zcalcd. for C 32 H 30 FN 2 O 5 [M+H] + : 541.2133, found 541.2134. (E)-ethyl-3-(3-(4-((2-cyanophenyl)(2-fluorophenyl)amino)-4-oxobutan-2-yl)phe nyl)acrylate (3b mono ): 1 H NMR (400 MHz, CDCl 3 ) δ 7.70 (d, J = 7.6 Hz, 1 H), 7.64 (d, J = 16.0 Hz, 1 H), 7.54 (t, J = 7.6 Hz, 1 H), 7.38-7.36 (m, 3 H), 7.31-7.24 (m, 4 H), 7.20-7.17 (m, 3 H), 6.39 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H)3.48 (m, 1 H), 2.65-2.49 (m, 2 H), 1.34 (m, 6 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.04, 167.10, 158.15 (d, J C-F = 254.6 Hz), 146.84, 144.75, 142.95, 134.71, 133.82 (d, J C-F = 43.4 Hz), 130.91, 129.15, 128.49, 128.36, 128.21, 127.91, 126.70, 126.14, 125.60, 119.87, 118.32, 117.43, 117.22, 112.98, 60.56, 42.47, 36.38, 21.50, 14.43; HRMS (EI-TOF): m/zcalcd. for C 28 H 26 FN 2 O 3 [M+H] + : 457.1922, found 457.1923. (2E,2'E)-diethyl-3,3'-(5-(4-((2-cyanophenyl)(2-fluorophenyl)amino)-4-oxobutan -2-yl)-1,3-phenylene)diacrylate (3b di ): 1 H NMR (400 MHz, CDCl 3 ) δ 7.68 (d, J = 8.0 Hz, 1 H), 7.63 (d, J = 16.0 Hz, 2 H), 7.53-7.50 (m, 3 H), 7.40-7.35 (m, 2 H), 7.28-7.26 (m, 2 H), 7.22 (m, 3 H), 6.42 (d, J = 16.0 Hz, 2 H), 4.27 (q, J = 7.2 Hz, 4 H) 3.50 (m, 1 H), 2.65-2.50 (m, 2 H), 1.33 (m, 9 H); 13 C NMR (100 MHz, CDCl 3 ) δ 171.83, 166.86, 158.14 (d, J C-F = 251.1 Hz), 147.53, 144.56, 143.88, 135.44, S22

133.85(d, J C-F = 49.5 Hz), 131.04, 129.00, 128.41, 127.98, 125.78, 119.32, 117.49, 117.30, 112.94, 60.72, 42.30, 36.39, 21.58, 14.42; HRMS (EI-TOF): m/zcalcd. for C 33 H 31 FN 2 NaO 5 [M+Na] + : 577.2109, found 577.2108. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-4-meth ylphenyl)acrylate (3c): 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (dd, J = 7.6, 1.2 Hz, 1 H), 7.60 (d, J = 15.6 Hz, 1 H), 7.58 (td, J = 7.2, 1.2 Hz, 1 H), 7.45-7.39 (m, 3 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 1 H), 7.22-7.20 (m, 3 H), 7.12 (d, J = 7.6 Hz, 1 H),6.35 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.05 (t, J = 8.0 Hz, 2 H), 2.57 (t, J = 7.6 Hz, 2 H), 2.23 (s, 3 H), 1.34 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.70, 167.27, 158.22 (d, J C-F = 246.8 Hz), 144.76, 144.56, 139.60, 139.00, 133.84 (d, J C-F = 51.5 Hz), 132.56, 131.00, 130.72, 129.54, 128.92, 128.81, 127.96, 126.10, 125.73, 119.08, 117.46 (d, J C-F = 19.1 Hz),116.98, 113.08, 60.50, 34.58, 28.67, 19.27, 14.46; HRMS (EI-TOF): m/zcalcd. for C 28 H 26 FN 2 O 3 [M+H] + : 457.1922, found 457.1921. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-4-meth oxyphenyl)acrylate (3d): 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (d, J = 7.6 Hz, 1 H), 7.60 (d, J = 16.0 Hz, 1 H), 7.59 (t, J = 7.6 Hz, 1 H), 7.44-7.30 (m, 6 H), S23

7.19-7.18(m, 2 H), 6.77 (d, J = 8.4 Hz, 1 H), 6.28 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 2 H), 3.73 (s, 3 H), 3.02 (t, J = 7.6 Hz, 2 H), 2.59 (t, J = 7.2 Hz, 2 H), 1.32 (t, J = 7.2Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 173.16, 167.49, 159.42, 158.22 (d, J C-F = 240.7 Hz), 144.79, 144.39, 133.81 (d, J C-F = 42.7 Hz), 130.85, 129.99, 129.64, 129.04, 128.38, 127.86, 127.01, 125.48, 117.29, 117.08, 115.83, 113.03, 110.44, 60.38, 55.35, 33.91, 26.58, 14.46; HRMS (EI-TOF): m/zcalcd. for C 28 H 26 FN 2 O 4 [M+H] + : 473.1871, found 473.1871. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-4-fluor ophenyl)acrylate (3e): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72(d, J = 7.6 Hz, 1 H), 7.59 (d, J = 16.0 Hz, 1 H), 7.60(t, J = 7.2 Hz, 1 H), 7.48 (t, J = 8.4 Hz, 1 H), 7.39-7.32(m, 5 H), 7.21-7.20 (m, 2 H), 6.98 (t, J = 7.2 Hz, 1 H), 6.33 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.07(t, J = 7.6 Hz, 2 H), 2.63 (s, 2 H), 1.33(t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) 172.33, 167.00, 162.33 (d, J C-F = 249.2 Hz), 158.18 (d, J C-F = 247.4 Hz), 144.65, 143.45, 142.27 133.82 (d, J C-F = 52.6 Hz), 131.08, 131.03, 130.80 (d, J C-F = 3.6 Hz), 130.69, 129.28 (d, J C-F = 13.2 Hz), 128.89, 128.31(d, J C-F = 16.4 Hz), 127.94,125.68, 118.06, 117.33 (d, J C-F = 19.6 Hz), 116.94, 115.99 (d, J C-F = 22.7 Hz), 114.99 (d, J C-F = 22.4 Hz), 112.98, 60.58, 34.14, 24.82, 14.40; HRMS (EI-TOF): m/zcalcd. for C 27 H 23 F 2 N 2 O 3 [M+H] + : 461.1671, found 473.1670. S24

(E)-ethyl-3-(4-chloro-3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropy l)phenyl)acrylate (3f): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.59 (d, J = 16.0 Hz, 1 H), 7.58(t, J = 7.2 Hz, 1 H), 7.47-7.38 (m, 4 H), 7.32 (d, J = 8.4Hz, 1 H),7.30(s, 2 H),7.20 (m, 2 H), 6.39 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 2 H), 3.16 (t, J = 7.6 Hz, 2 H), 2.64 (t, J = 7.2 Hz, 2 H), 1.33 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.38, 166.85, 158.24 (d, J C-F = 248.8 Hz), 144.70, 143.25,141.96,138.96, 135.88, 133.82 (d, J C-F = 50.3 Hz), 133.51,130.92, 130.76, 130.65, 130.08, 129.13, 128.91, 127.96, 127.17, 125.68, 119.05, 117.34 (d, J C-F = 19.5 Hz), 116.95, 113.05, 60.66, 33.78, 29.36, 14.41; HRMS (EI-TOF): m/zcalcd. for C 27 H 23 ClFN 2 O 3 [M+H] + : 477.1376, found 477.1379. (E)-ethyl-3-(4-bromo-3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropy l)phenyl)acrylate (3g): 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (d, J = 7.2 Hz, 1 H), 7.57 (d, J = 16.0 Hz, 1 H), 7.58 (s, 1 H), 7.48 (d, J = 8.4 Hz, 2 H), 7.47-7.40 (m, 3 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.22-7.20 (m, 3 H), 6.40 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 2 H), 3.16 (t, J = 8.0 Hz, 2 H), 2.65 (s, 2 H), 1.33 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.18, 166.70, 158.24 (d, J C-F = 249.5 Hz), 144.51, 143.13, 141.82, 140.54, 133.66 (d, J C-F = 50.9 Hz), 133.26, 130.76, 130.60, 130.39, 129.91, 129.25,128.73, 127.80, 127.11, 126.15,125.55, 118.98, 117.19 (d, J C-F = 19.5 Hz), 116.78, 112.85, 60.53, 33.73, 31.62, 14.24;HRMS (EI-TOF): m/zcalcd. S25

for C 27 H 23 BrFN 2 O 3 [M+H] + : 521.0871, found 521.0870. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-4-(trifl uoromethyl)phenyl)acrylate (3 H): 1 H NMR (400 MHz, CDCl 3 ) δ 7.74 (dd, J = 8.0, 1.6 Hz, 1 H), 7.64(d, J = 16.4 Hz, 1 H), 7.58 (d, J = 8.0 Hz, 2 H),7.48-7.34 (m, 6 H), 7.20 (m, 2 H), 6.48 (d, J = 16.4 Hz, 1 H), 4.27 (q, J = 7.2 Hz, 2 H), 3.23 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 2 H), 1.35 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.19, 166.51, 158.16 (d, J C-F = 248.1 Hz), 144.65, 142.65, 140.29, 138.08, 135.89, 133.83 (d, J C-F = 56.8 Hz), 131.13, 130.63, 129.89, 129.59, 129.24, 128.84, 126.78 (q, J C-F = 248.1 Hz ), 126.42, 126.74 (q, J C-F = 5.6 Hz), 125.72,122.83, 121.02, 117.31 (d, J C-F = 19.8 Hz), 116.94, 112.99, 60.83, 35.84, 28.08, 14.36;HRMS (EI-TOF): m/zcalcd. for C 28 H 23 F 4 N 2 O 3 [M+H] + : 511.1639, found 511.1640. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-meth ylphenyl)acrylate (3i): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.60 (d, J = 16.0 Hz, 1 H), 7.58 (td, J = 7.2, 1.6 Hz, 1 H), 7.45-7.38 (m, 3 H), 7.31 (d, J = 7.6 Hz, 1 H), 7.23-7.14 (m, 3 H), 7.06 (s, 1 H), 6.99 (s, 1 H), 6.38 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 2 H), 3.01 (t, J = 7.6 Hz, 2 H), 2.60 (t, J = 7.2 Hz, S26

2 H), 2.31 (s, 3 H), 1.33 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.69, 167.23, 158.23 (d, J C-F = 250.4 Hz), 144.79, 141.48, 138.88, 134.71, 133.85 (d, J C-F = 49.1 Hz), 133.61, 131.55, 130.93 (d, J C-F = 7.7 Hz), 130.79, 128.96, 127.96, 126.78, 125.66, 125.45, 119.33, 118.18, 117.36 (d, J C-F = 20.2 Hz), 117.00, 113.05, 60.57, 35.94, 30.93, 21.34, 14.45; HRMS (EI-TOF): m/zcalcd. for C 28 H 23 F 4 N 2 O 3 [M+H] + :457.1922, found 457.1923. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-meth oxyphenyl)acrylate (3j): 1 H NMR (400 MHz, CDCl 3 ) δ7.73 (d, J = 7.6 Hz, 1 H), 7.58 (d, J = 16.0 Hz, 1 H), 7.58 (td, J =8.0, 1.6 Hz, 1 H), 7.46-7.38 (m, 3 H), 7.31(d,J = 8.0 Hz, 1 H), 7.23-7.15 (m, 2 H), 6.87 (s, 2 H), 6.72 (s, 1 H), 6.37 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.79 (s, 3 H), 3.02 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 2 H), 1.34 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.55, 167.06, 160.15, 158.22 (d, J C-F = 249 Hz), 144.75, 144.57, 143.03, 135.97,133.85 (d, J C-F = 49.4 Hz), 130.95, 130.78, 129.34, 128.94, 127.96, 125.72, 122.75,121.09, 118.71, 117.38 (d, J C-F = 19.8 Hz), 116.99, 116.48, 113.07, 110.89, 60.63, 55.45, 35.85, 31.13, 14.45; HRMS (EI-TOF): m/zcalcd. for C 28 H 25 FN 2 NaO 4 [M+Na] + : 495.1691, found 495.1692. S27

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3k): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.59-7.55 (m, 2 H), 7.40-7.38 (m, 3 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.26-7.21 (m, 2 H), 7.06 (s, 1 H), 7.03 (s, 1 H), 6.88 (d, J = 8.8 Hz, 1 H), 6.38 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.04 (t, J = 7.2 Hz, 2 H), 2.63 (t, J = 7.2 Hz, 2 H), 1.34 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.26, 166.79, 163.14 (d, J C-F = 245.1 Hz), 158.20 (d, J C-F = 251.0 Hz), 144.66, 143.98(d, J C-F = 7.9 Hz), 143.36, 136.73 (d, J C-F = 8.2 Hz), 133.88 (d, J C-F = 54.8 Hz), 131.10 (d, J C-F = 9.3 Hz), 130.73, 129.26,128.92, 128.06, 125.79, 124.45 (d, J C-F = 2.1 Hz), 121.12, 119.75, 117.42 (d, J C-F = 20.8Hz), 117.32 (d, J C-F = 21.3 Hz), 116.99,113.05, 112.19 (d, J C-F =22.0 Hz), 60.78, 35.47, 30.73, 14.43; HRMS (EI-TOF): m/zcalcd. for C 27 H 23 F 2 N 2 O 3 [M+H] + : 461.1671, found 461.1675. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3l): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.58 (td, J = 8.0, 1.2 Hz, 1 H), 7.55 (d, J = 16.0 Hz, 1 H), 7.47-7.38 (m, 3 H), 7.33-7.30 (m, 2 H), 7.23-7.21 (m, 2 H), 7.16 (s, 1 H), 7.13 (s, 1 H), 6.39 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.03 (t, J = 7.2 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 2 S28

H), 1.33 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.24, 166.74, 158.19 (d, J C-F = 247.9 Hz), 144.66, 143.42, 143.10, 136.43, 134.93, 133.88 (d, J C-F = 54.2 Hz), 131.14, 130.71, 130.28, 129.21, 128.90, 128.05, 126.74, 125.74, 120.95, 119.85, 117.43 (d, J C-F = 20.6 Hz), 116.99, 113.02, 60.79, 35.48, 30.66, 14.42; HRMS (EI-TOF): m/zcalcd. for C 27 H 23 ClFN 2 O 3 [M+H] + : 477.1376, found 477.1377. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3m): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.59 (d,j = 7.2 Hz, 1 H), 7.54 (d, J = 16.0 Hz, 1 H), 7.49-7.38 (m, 4 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.28 (s, 1 H), 7.23-7.21 (m, 3 H), 6.39 (d, J = 15.6 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.02 (t, J = 7.2 Hz, 2 H), 2.62 (t, J = 7.2 Hz, 2 H), 1.33 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.18, 166.65, 158.18 (d, J C-F = 249.1 Hz), 144.66, 143.67, 142.94, 141.10, 136.71, 133.86 (d, J C-F = 53.7 Hz),133.13, 131.04, 130.71, 129.29 (d, J C-F = 13.7 Hz), 128.91,128.68, 128.02,127.17, 125.75, 123.08, 119.90, 117.41 (d, J C-F = 21.3 Hz), 116.95, 113.04, 60.76, 35.49, 30.64, 14.41;HRMS (EI-TOF): m/zcalcd. for C 27 H 23 BrFN 2 O 3 [M+H] + : 521.0871, found 521.0870. S29

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3n): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.64 (d, J = 16.0 Hz, 1 H), 7.59-7.56 (m,2 H), 7.48-7.38 (m, 5 H), 7.29 (d, J = 8.0 Hz, 1 H), 7.22-7.21 (m, 2 H), 6.46 (d, J = 16.4 Hz, 1 H), 4.27 (q, J = 7.2 Hz, 2 H), 3.11 (t, J = 7.2 Hz, 2 H), 2.64 (t, J = 7.2 Hz, 2 H), 1.34 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.11, 166.60, 158.21 (d, J C-F = 248.8 Hz), 144.66, 142.92, 142.69, 141.23, 135.63, 133.89 (d, J C-F = 55.2Hz), 132.17, 131.85, 131.56, 130.71, 128.90, 128.08, 126.77 (q, J C-F = 3.6 Hz), 125.80, 125.26, 122.64, 122.55, 120.38, 117.43 (d, J C-F = 20.5 Hz), 116.95, 113.06, 60.85, 35.43, 30.78, 14.42; HRMS (EI-TOF): m/zcalcd. for C 28 H 22 F 4 N 2 NaO 3 [M+Na] + : 533.1459, found 533.1460. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3o): 1 H NMR (400 MHz, CDCl 3 ) δ 7.91 (d, J = 16.0 Hz, 1 H), 7.72 (d, J = 6.8 Hz, 1 H), 7.58 (td, J = 8.0, 1.2 Hz, 1 H), 7.44-7.34 (m, 3 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.22-7.13 (m, 4 H), 6.81 (d, J = 8.4 Hz, 1 H), 6.47 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.85 (s, 3 H), 2.98 (t, J = 7.2 Hz, 2 H), 2.58 (t, J = 7.6 Hz, 2 H), 1.34 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.73, 167.66, 158.21 (d, J C-F = 253.5 Hz), 157.02, 144.74, 140.05, 138.67, 133.85 (d, J C-F = 48.0 Hz),132.95, 131.63, 130.94, 130.80, 129.37, 128.92, 127.95, 125.65, 123.40, 120.35, 118.93, 117.36 (d, J C-F = 18.2 Hz), 116.99, 113.04, 111.39, 60.45, 55.69, 36.21, 30.22, 14.50; HRMS (EI-TOF): m/zcalcd. for C 28 H 25 FN 2 NaO 4 [M+Na] + : 495.1691, found 495.1694. S30

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3p): 1 H NMR (400 MHz, CDCl 3 ) δ 7.74 (d, J = 16.0 Hz, 1 H), 7.73 (d, J = 8.0 Hz, 1 H), 7.58 (t, J = 7.2 Hz, 1 H), 7.47-7.38 (m, 3 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.27 (dd, J = 6.8, 2.4 Hz, 1 H), 7.22-7.12 (m, 3 H), 6.98 (d, J = 8.4 Hz, 1 H), 6.49 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.2 Hz, 2 H), 3.02 (t, J = 7.6 Hz, 2 H), 2.60 (t, J = 7.2 Hz, 2 H), 1.34 (t, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.40, 166.96, 160.14 (d, J C-F = 251.0 Hz), 158.22 (d, J C-F = 251.4 Hz), 144.69, 137.35, 137.00, 135.42, 133.87 (d, J C-F = 53.4 Hz), 131.88 (d, J C-F = 8.5 Hz),131.07, 130.73, 129.98, 129.33, 129.02 (d, J C-F = 2.9 Hz), 128.91, 128.01, 125.72, 122.56, 122.40 (d, J C-F = 11.8 Hz), 120.95 (d, J C-F = 6.6 Hz), 117.38 (d, J C-F = 18.4 Hz), 116.99, 116.26 (d, J C-F = 21.9 Hz), 113.04, 60.70, 35.88, 30.24, 14.43; HRMS (EI-TOF): m/zcalcd. for C 27 H 23 F 2 N 2 O 3 [M+H] + : 461.1671, found 461.1670. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3q): 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (d, J = 7.6 Hz, 1 H), 7.60 (d, J = 16.0 Hz, 1 H), 7.59 (td, J = 8.0, 1.6 Hz, 1 H), 7.45-7.38 (m, 3 H), 7.32 (d, J = 8.4 Hz, 1 H), 7.24-7.20 (m, 2 H), 6.87 (s, 2 H), 6.73 (s, 1 H), 6.38 (d, J = 16.0 Hz, 1 H), 3.81 (s, 3 H), 3.79 (s, 3 H), 3.03 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.55, 167.52, 160.12, 158.22 (d, J C-F = S31

248.9 Hz), 144.88, 144.72, 143.05, 135.86, 133.85 (d, J C-F = 51.7 Hz), 130.96, 130.77, 129.31, 128.92, 127.98, 125.69, 121.07, 118.19, 117.38 (d, J C-F = 19.8 Hz), 117.00, 116.50, 113.03, 110.97, 55.46, 51.86, 35.84, 31.11; HRMS (EI-TOF): m/zcalcd. for C 27 H 24 FN 2 O 4 [M+H] + : 459.1715, found 459.1716. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3r): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.2 Hz, 1 H), 7.58 (d, J = 16.0 Hz, 1 H), 7.58 (d, J = 6.4, 1.2 Hz, 1 H), 7.46-7.38 (m, 3 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.23-7.14 (m, 2 H), 6.87 (s, 2 H), 6.72 (s, 1 H), 6.38 (d, J = 16.0 Hz, 1 H), 4.20 (t,j = 6.8 Hz, 2 H), 3.79 (s, 3 H), 3.02 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 2 H),1.72-1.65 (m, 2 H), 1.48-1.41 (m, 2 H), 0.96 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.58, 167.19, 160.12, 158.21 (d, J C-F = 248.5 Hz), 144.70, 144.55, 143.01, 135.96, 133.85 (d, J C-F = 50.9 Hz), 131.03, 130.77, 128.93, 128.37, 127.97, 125.68, 121.09, 118.69, 117.37 (d, J C-F = 19.6 Hz), 117.00, 116.49,, 113.02, 110.86, 64.57, 55.45, 35.85, 31.12, 30.88, 19.32, 13.88; HRMS (EI-TOF): m/zcalcd. for C 30 H 30 FN 2 O 3 [M+H] + : 485.2235, found 485.2234. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor S32

ophenyl)acrylate (3s): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (td, J = 8.0, 1.6 Hz, 1 H), 7.56 (d, J = 15.6 Hz, 1 H), 7.44-7.38 (m, 3 H), 7.31 (d, J = 7.6 Hz, 1 H), 7.23-7.18 (m, 2 H), 6.90 (s, 1 H), 6.86 (s, 1 H), 6.82 (s, 1 H), 6.67 (s, 1 H), 3.79 (s, 3 H), 3.17 (s, 3 H), 3.07 (s, 3 H), 3.02 (t, J = 8.0 Hz, 2 H), 2.61 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.58, 166.74, 160.06, 158.20 (d, J C-F = 249.1 Hz), 144.71, 142.85, 142.22, 137.81, 136.90, 133.82 (d, J C-F = 53.5 Hz), 130.92, 130.73, 129.29, 128.87, 127.92, 125.65, 120.36, 117.93, 117.34 (d, J C-F = 19.8 Hz), 117.00, 115.38, 113.00, 111.40, 55.43, 37.57, 36.04, 35.94, 31.21;HRMS (EI-TOF): m/zcalcd. for C 28 H 27 FN 3 O 3 [M+H] + : 472.2031, found 472.2031. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3t): 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (td, J = 8.0, 1.2 Hz, 1 H), 7.56 (d, J = 16.4 Hz, 1 H), 7.43-7.38 (m, 3 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.21-7.15 (m, 2 H), 6.91 (s, 1 H), 6.89 (s, 1 H), 6.72 (s, 1 H), 6.68 (d, J = 16.4Hz, 1 H), 3.79 (s, 3 H), 3.03 (t, J = 7.6 Hz, 2 H), 2.69 (q, J = 7.2 Hz, 2 H), 2.61 (t, J = 7.6 Hz, 2 H), 1.16 (t, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ201.12, 172.57, 160.15, 158.29 (d, J C-F = 264.5 Hz), 144.72, 143.08, 142.27, 136.11, 133.87 (d, J C-F = 53.4 Hz), 131.04, 130.76, 129.30, 128.90, 128.00, 126.41, 125.72, 121.29, 117.48, 117.16 (d, J C-F = 26.1 Hz), 116.62, 113.02, 111.01, 55.47, 35.82, 34.14, 31.06, 8.35;HRMS (EI-TOF): m/zcalcd. for C 28 H 26 FN 2 O 3 [M+H] + : 457.1922, found 457.1921. S33

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3u): 1 H NMR (400 MHz, CDCl 3 ) δ 9.68 (d, J = 8.0 Hz, 1 H), 7.72 (d, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.2 Hz, 1 H), 7.41 (d, J = 22.8 Hz, 1 H), 7.46-7.38 (m, 3 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.24-7.20 (m, 2 H), 6.93 (s, 1 H), 6.91 (s, 1 H), 6.78 (s, 1 H),6.68 (dd, J = 16.0, 7.6Hz, 1 H), 3.80 (s, 3 H), 3.05 (t, J = 7.6 Hz, 2 H), 2.63 (t, J = 7.2 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ193.88, 172.45, 160.23, 158.21 (d, J C-F = 248.4 Hz), 152.94, 144.70, 143.35, 135.48, 133.87 (d, J C-F = 54.9 Hz), 131.00, 130.75, 129.31, 128.91, 128.02, 125.73, 121.67, 117.50,117.39 (d, J C-F = 21.8 Hz), 113.04, 111.17, 55.51, 35.70, 30.96; HRMS (EI-TOF): m/zcalcd. for C 26 H 22 FN 2 O 3 [M+H] + : 429.1609, found 429.1608. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3v): 1 H NMR (400 MHz, CDCl 3 ) δ7.72 (dd, J = 7.6, 1.2 Hz, 1 H), 7.58 (td, J = 7.2, 1.6 Hz, 1 H), 7.47-7.33 (m, 3 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.21-7.19 (m, 2 H), 6.80 (s, 2 H), 6.69 (s, 1 H), 6.08 (q, J = 1.2 Hz, 1 H), 3.79 (s, 3 H), 3.76 (s, 3 H), 3.03 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.6 Hz, 2 H), 2.52 (t, J = 1.6 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.64, 167.37, 159.89, 158.08 (d, J C-F = 249.3 Hz), 155.89, 144.76, 143.90, 142.67, 133.87 (d, J C-F = 47.5 Hz), 130.95, S34

130.81, 128.97, 128.88, 127.98, 125.69, 119.47, 119.10, 117.37 (d, J C-F = 20.6 Hz), 116.94, 114.95, 114.76, 113.10, 110.20, 55.49, 51.27, 36.06, 31.40, 21.71, 18.24; HRMS (EI-TOF): m/zcalcd. for C 29 H 27 FN 2 NaO 4 [M+Na] + : 509.1847, found 509.1840. (E)-N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-methoxy-5-(4-oxopent-2-en-2-yl )phenyl)propanamide (3w): 1 H NMR (400 MHz, CDCl 3 ) δ7.73 (dd, J = 7.6, 1.2 Hz, 1 H), 7.58 (t, J = 7.6, Hz, 1 H), 7.45-7.37 (m, 3 H), 7.33-7.29 (m, 2 H),7.14-7.26 (m, 4 H), 6.47 (s, 1 H), 3.07 (t, J = 7.6 Hz, 2 H), 2.63 (t, J = 7.6 Hz, 2 H), 2.49 (d, J = 1.2 Hz, 3 H), 2.29 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ199.12, 172.65, 158.26 (d, J C-F = 250.0 Hz), 153.93, 144.76, 142.88, 141.25, 133.88 (d, J C-F = 49.2 Hz), 131.00, 130.92, 130.81, 129.36, 128.95, 128.90, 128.84, 128.00, 126.75, 125.68, 124.66, 124.60, 117.36 (d, J C-F = 18.6 Hz), 116.97, 113.08, 36.08, 32.39, 31.41, 31.20, 18.50; HRMS (EI-TOF): m/zcalcd. for C 28 H 25 FN 2 NaO 3 [M+Na] + : 479.1747, found 479.1748. Dimethyl-2-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-meth oxyphenyl)maleate (3x): 1 H NMR (400 MHz, CDCl 3 ) δ7.71 (d, J = 7.6Hz, 1 H), 7.57 (t, J = 7.6 Hz, 1 H), 7.46-7.32 (m, 4 H), 7.22-7.18 (m, 2 H), 6.97 (s, 1 H), 6.65 (d, J = 1.2 Hz, 1 H), 6.62 (s, 1H), 6.58 (s, 1 H), 3.78 (s, 3H), 3.74 (s, 3H), 3.56 (s, S35

3H),3.02 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ172.64, 166.69, 165.58, 159.17,158.17 (d, J C-F = 249.2 Hz), 144.70, 143.66, 141.82,135.04, 133.75 (d, J C-F = 48.9 Hz), 130.80, 129.99, 129.30, 128.87, 127.85,125.60,124.85, 121.38, 119.37, 117.27 (d, J C-F = 20.3 Hz), 116.93, 114.44, 112.97,112.50, 55.29, 52.98, 51.91, 35.89, 31.19; HRMS (EI-TOF): m/zcalcd. for C 29 H 25 FN 2 NaO 6 [M+Na] + : 539.1594, found 539.1590. Dimethyl-2-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-methox yphenyl)fumarate (3y): 1 H NMR (400 MHz, CDCl 3 ) δ7.71 (d, J = 7.6Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.44-7.35 (m, 3 H),7.30 (d, J = 7.6Hz, 1 H), 7.26-7.19 (m, 2 H), 6.81 (s, 2 H), 6.76 (s, 1H), 6.25 (s, 1 H), 3.91 (s, 3H), 3.77 (s, 3H), 3.77 (s, 3H),3.02 (t, J = 7.6 Hz, 2 H), 2.60 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ172.37, 168.27, 165.44, 160.12,158.12 (d, J C-F = 248.8 Hz), 148.91, 144.61,143.29, 134.32 (d, J C-F = 52.0 Hz), 133.51, 130.98 (d, J C-F = 6.7 Hz),130.67, 129.92, 129.26 (d, J C-F = 12.4 Hz), 128.85, 127.91, 125.65, 124.89, 119.35, 117.41, 117.07 (d, J C-F = 29.0 Hz), 116.50, 112.92, 110.37, 55.45, 52.82, 52.13, 35.79, 31.15;HRMS (EI-TOF): m/zcalcd. for C 29 H 25 FN 2 NaO 6 [M+Na] + : 539.1594, found 539.1592. S36 (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor

ophenyl)acrylate (3z): 1 H NMR (400 MHz, CDCl 3 ) δ7.72 (d, J = 7.2 Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.47-7.30 (m, 5 H), 7.23-7.19 (m, 2 H), 6.85 (s, 2 H), 6.71(s, 1 H), 6.19 (t, J = 17.6 Hz, 1 H), 4.12(td, J = 7.6, 1.6 Hz, 4 H), 3.78 (s, 3 H), 3.01 (t, J = 7.6 Hz, 2 H), 2.60 (t, J = 7.6 Hz, 2 H), 1.35 (t, J = 7.2 Hz, 6 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.56, 160.13, 158.20 (d, J C-F = 249.0 Hz), 148.70, 144.71, 143.02, 136.47, 136.23, 133.85 (d, J C-F = 53.2 Hz), 130.73, 129.40, 128.90,127.97, 125.72, 120.56, 117.39 (d, J C-F = 19.0 Hz), 117.00, 116.39, 115.26, 113.36, 113.00, 110.77, 62.03, 55.46, 35.82, 31.16, 16.56; HRMS (EI-TOF): m/zcalcd. for C 29 H 31 FN 2 O 5 P [M+H] + : 537.1949, found 537.1950. (E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3α): 1 H NMR (400 MHz, CDCl 3 ) δ7.72 (dd, J = 7.6, 1.6 Hz, 1 H), 7.57 (td, J = 7.6, 1.6 Hz, 1 H), 7.48-7.31 (m, 6 H), 7.22-7.18 (m, 2 H), 7.07-7.00 (m, 3 H), 6.95-6.86 (m, 3 H), 6.59 (s, 1 H), 3.80 (s, 3 H), 3.04 (t, J = 7.6 Hz, 2 H), 2.63 (t, J = 7.6 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.81, 162.51 (d, J C-F = 245.8 Hz),160.17, 158.23 (d, J C-F = 247.1 Hz), 144.81, 142.76, 138.79, 133.86 (d, J C-F = 49.1 Hz), 133.56, 133.53,130.86, 129.59, 129.41, 128.99, 128.43, 128.15 (d, J C-F = 7.9 Hz), 127.97, 125.63, 121.71, 119.52, 117.36 (d, J C-F = 18.9 Hz), 117.04, 115.77 (d, J C-F = 21.6 Hz), 113.70, 113.09, 109.76, 55.43, 36.09, 31.37;H HRMS (EI-TOF): m/zcalcd. for C 31 H 25 F 2 N 2 O 2 [M+H] + : 495.1879, found 495.1881. S37

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-fluor ophenyl)acrylate (3β): 1 H NMR (400 MHz, CDCl 3 ) δ 7.96-7.93 (m, 2 H), 7.71 (d, J = 7.6Hz, 1 H), 7.63-7.54 (m, 5 H), 7.44-7.38 (m, 3 H), 7.29 (d, J = 8.0 Hz, 1 H), 7.23-7.18 (m, 2 H), 6.84 (s, 1 H), 6.81 (d, J = 15.6 Hz, 1 H), 6.81 (s, 1 H), 6.75 (s, 1 H), 3.77 (s, 3 H), 3.00 (t, J = 7.6 Hz, 2 H), 2.59 (t, J = 7.2 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.43, 160.21, 158.19 (d, J C-F = 248.4 Hz), 144.67, 143.36, 142.55, 140.79, 133.87 (d, J C-F = 56.8 Hz), 133.79, 133.53, 131.01, 130.73, 129.47, 129.25, 128.87, 128.02, 127.81, 127.73, 127.63, 125.74, 121.34, 117.46, 117.38 (d, J C-F = 17.0 Hz), 116.99, 113.00, 111.60, 55.52, 35.64, 30.97; HRMS (EI-TOF): m/zcalcd. for C 31 H 26 FN 2 O 4 S [M+H] + : 541.1592, found 541.1593. (E)-ethyl-3-(1-(3-(4-cyano-2,6-dimethylheptan-4-yl)-4-methoxyphenylsulfonyl)i ndolin-6-yl)acrylate (6a): 6 was olefinated following the general procedure in the absence of added TFA to provide 6a. 1 H NMR (400 MHz, CDCl 3 ) δ 8.05 (d, J = 2.4 Hz, 1 H), 7.79 (dd, J = 8.8, 2.4 Hz, 1 H), 7.77 (s, 1 H), 7.65 (d, J = 16.0 Hz, 1 H), 7.12 (dd, J= 8.0, 1.2 Hz, 1 H), 7.06 (d, J = 7.6 Hz, 1 H), 6.90 (d, J = 8.8 Hz, 1 H), 6.45 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2Hz, 2 H), 3.98 (q, J = 8.4 Hz, 2 H), 3.85 S38

(s, 3 H), 2.92 (t, J = 8.4 Hz, 2 H), 2.17 (dd, J = 14.0, 6.0 Hz, 2 H), 1.72-1.67 (m, 3 H), 1.33 (t, J = 7.2 Hz, 3 H), 0.81 (d, J = 6.8 Hz, 6 H), 0.47 (d, J = 6.4 Hz, 6 H); 13 C NMR (100 MHz, CDCl 3 ) δ167.13, 161.20, 144.26, 142.68, 134.84, 134.21, 129.42, 126.70, 125.49, 124.36, 123.16, 118.70, 113.87, 111.60, 60.61, 55.81, 50.50, 46.99, 46.70, 27.92, 25.90, 23.58, 23.55, 14.44. (E)-ethyl-3-(3-(3-(4-cyano-2,6-dimethylheptan-4-yl)-4-methoxy-N-methylpheny lsulfonamido)phenyl)acrylate (7a mono ): 7 was olefinated following the general procedure to provide 7a mono and 7a di. 1 H NMR (400 MHz, CDCl 3 ) δ 7.88 (d, J = 2.4 Hz, 1 H), 7.57 (d, J = 16.0 Hz, 1 H), 7.50 (dd, J = 8.8, 2.4 Hz, 1 H), 7.45-7.40(m, 1 H), 7.32 (t, J = 8.8 Hz, 1 H), 7.21-7.17 (m, 2 H), 6.88 (d, J = 8.4 Hz, 1 H), 6.32 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2Hz, 2 H), 3.90 (s, 3 H), 3.23 (s, 3 H), 2.25 (dd, J = 14.0, 6.0Hz, 2 H), 1.75 (dd, J = 7.6, 6.4 Hz, 2 H), 1.49-1.44 (m, 2 H), 1.32 (t, J = 7.2 Hz, 3 H), 0.92 (d, J = 6.8 Hz, 6 H), 0.62 (d, J = 6.8 Hz, 6 H); 13 C NMR (100 MHz, CDCl 3 ) δ 166.75, 160,85, 43.65, 142.25, 135.53, 129.98, 129.63, 129.34, 128.87, 128.72, 128.11, 126.78, 126.61, 126.05, 125.41, 123.16, 119.41, 111.35, 60.73, 55.83, 47.01, 46.84, 38.14, 25.99, 23.75, 23.72, 14.42. S39

(2E,2'E)-diethyl-3,3'-(5-(3-(4-cyano-2,6-dimethylheptan-4-yl)-4-methoxy-N-met hylphenylsulfonamido)-1,3-phenylene)diacrylate (7a di ): 7 was olefinated following the general procedure to provide 7a mono and 7a di. 1 H NMR (400 MHz, CDCl 3 ) δ 7.91 (d, J = 2.0 Hz, 1 H), 7.57 (d, J = 16.0 Hz, 2 H), 7.52 (s, 1 H), 7.49(dd, J = 8.4, 2.4 Hz, 1 H), 7.27 (d, J = 1.6 Hz, 1 H),7.26 (s, 1 H), 6.89 (d, J = 8.8 Hz, 1 H), 6.37 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 4 H), 3.90 (s, 3 H), 3.24 (s, 3 H), 2.26 (dd, J = 14.4, 6.0Hz, 2 H), 1.76 (dd, J = 14.4, 6.8 Hz, 2 H), 1.49-1.44 (m, 2 H), 1.33 (t, J = 7.2 Hz, 6 H), 0.92 (d, J = 6.4 Hz, 6 H), 0.62 (d, J = 6.8 Hz, 6 H); 13 C NMR (100 MHz, CDCl 3 ) δ 166.52, 160.98, 142.91, 142.86, 136.17, 130.03, 129.26, 128.65, 126.78, 126.70, 126.08, 123.14, 120.38, 111.41, 60.88, 55.87, 47.07, 46.80, 38.08, 26.03, 23.70, 14.42. 2.5 meta-c H Olefination of Indoline and N-Methylaniline 2.6 Kinetic Isotope Effect. Kinetic studies on the meta-olefination of 1a and 1a-D were conducted in separate vessels. To a 25 ml Schlenk-type sealed tube equipped with a magnetic stirring bar was added the substrate (0.1 mmol), [RhCp*Cl 2 ] 2 (3.1 mg, 0.005 mmol), S40

Yield (%) Cu(CO 2 CF 3 ) 2 xh 2 O (28.9 mg, 0.1 mmol), CF 3 CO 2 H (0.1 mmol), olefin (0.5 mmol) and DCE (2.0 ml). The tube was evacuated then back-filled with O 2 (3 times, balloon), capped, and immersed into a pre-heated oil bath at 100 C. After the indicated time, the Schlenk-type tube was cooled by ice water. The reaction mixture was filtered through Celite and eluted with DCM (4 4 ml). The filtrate was concentrated in vacuo to afford crude products. The yield was determined by 1H NMR analysis of the crude product using CH 2 Br 2 as an internal standard. Each time point was repeated three times and the equations for the lines were determined by linear regression. The ratio of the slopes for these lines corresponds to the KIE. 18 16 14 12 Eq. 1 Eq. 2 10 8 6 4 2 1 2 3 4 5 Time (h) S41

Table S10. Data from the Kinetic Isotope experiments with 1a and 1a-D S42

2.7 The procedure for the 10 mmol reaction in Toluene To a 250 ml round-bottom flask was added a magnetic stir bar, substrate 1a (10 mmol), [RhCp*Cl 2 ] 2 (0.31 g, 0.5 mmol), Cu (CO 2 CF 3 ) 2 xh 2 O (2.89 g, 10 mmol), CF 3 CO 2 H (1.14 g, 10 mmol), dry toluene (150 ml) and Ethyl acrylate (5.00 g, 50 mmol). The system was equipped with a reflux condenser and was evacuated and then back-filled with O 2 (balloon, 3 times). Next, the reaction was refluxed for 48 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and water and the phases were separated. The aqueous layer was extracted with ethyl acetate three times. The combined organic extracts were dried over MgSO 4, filtered and concentrated in vacuo to afford crude products, which were purified by flash column chromatography on silica gel using hexanes/etoac (3/1) as the eluent to give the pure products in 75% combined yield (mono 55%, di 20% isolated). S43

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1 H NMR of 3e at room temperature used d 6 -DMSO as solvent 1 H NMR of 3e at 100 d 6 -DMSO as solvent S97