Coordination Chemistry Institute, State Key Laboratory … Xu,† Yi Lu,*, ... ‡ Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California

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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

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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 CDCl3. 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 (T3)1

Toa 100 mL round bottom flask was added 2-fluorobenzonitrile (20 mmol,

1.0 equiv), 2-fluoroaniline (20 mmol, 1.0 equiv) and tBuOK (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.

2-(2-fluorophenylamino)benzonitrile (T3): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 155.31 (d, JC-F = 195.4 Hz), 146.54, 133.57 (d, JC-F = 83.5 Hz),

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128.20 (d, JC-F = 9.5 Hz), 124.98 (d, JC-F = 5.9 Hz), 124.65 (d, JC-F = 2.7 Hz),

122.72, 120.111, 117.34, 116.47 (d, JC-F = 15.5 Hz), 114.78, 99.62; HRMS

(EI-TOF): m/zCalcd. for C13H10FN2 [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 (T3) (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 0oC 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 oC. The

reaction was stirred overnight, then quenched with water, and extracted with DCM

three times.The combined organic extractsweredried over MgSO4 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): 1H NMR

(400 MHz, CDCl3) 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, CDCl3) δ 172.87, 158.25 (d, JC-F = 247.6 Hz), 144.80,

140.88, 133.85 (d, JC-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, JC-F = 20.7 Hz), 117.01, 113.10, 36.15,

31.21; HRMS (EI-TOF): m/zCalcd. for C22H18FN2O [M+H]+: 345.1398, found

345.1401.

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N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-phenylbutanamide (1b): 1H NMR (400

MHz, CDCl3) 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, CDCl3) δ 172.34, 158.81 (d, JC-F = 245.3 Hz), 146.07, 144.64, 133.82 (d,

JC-F = 38.8 Hz), 130.84, 129.46 (d, JC-F = 13.2 Hz), 129.08, 128.55, 127.85, 126.96,

126.39, 125.50, 124.79, 117.25 (d, JC-F = 20.5 Hz), 116.85, 112.97, 42.72, 36.36,

21.43; HRMS (EI-TOF): m/zCalcd. for C23H20FN2O [M+H]+: 359.1554, found

359.1552.

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-o-tolylpropanamide (1c): 1H NMR


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, CDCl3) δ 173.00, 157.75 (d, JC-F = 249.1

Hz), 144.82, 138.94, 136.18, 133.82 (d, JC-F = 47.6 Hz), 130.76, 130.37, 129.47,

129.01, 127.91, 126.50, 126.23, 125.65, 117.32 (d, JC-F = 20.7 Hz), 117.00, 113.09,

34.76, 28.80, 19.16; HRMS (EI-TOF): m/zCalcd. for C23H20FN2O [M+H]+:

359.1554, found 359.1556.

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(2-methoxyphenyl)propanamide (1d):

1H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 8.0, 1.2 Hz, 1 H), 7.58 (td, J = 8.0,

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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, CDCl3) δ 173.45, 158.25 (d, JC-F = 247.0 Hz), 157.58, 144.84, 133.76 (d,

JC-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, JC-F = 24.0 Hz), 116.98, 113.03, 110.20, 55.05, 34.14, 26.66;

HRMS (EI-TOF): m/zCalcd. for C23H20FN2O2 [M+H]+: 375.1503, found 375.1504.

N-(2-cyanophenyl)-N,3-bis(2-fluorophenyl)propanamide (1e): 1H NMR (400

MHz, CDCl3) 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,

CDCl3) δ 172.63, 161.22 (d, JC-F = 243.9 Hz), 158.22 (d, JC-F = 249.5 Hz),144.70,

133.81 (d, JC-F = 49.0 Hz), 130.92 (d, JC-F = 37.9 Hz), 130.89, 129.27, 128.93,

128.10 (d, JC-F = 7.7 Hz), 127.90, 127.55 (d, JC-F = 16.1 Hz), 125.63, 124.17 (d, JC-F

= 3.4 Hz), 117.29 (d, JC-F = 20.1 Hz),116.98, 115.27 (d, JC-F = 21.7 Hz), 112.99,

34.39, 24.91; HRMS (EI-TOF): m/zCalcd. for C22H17F2N2O [M+H]+: 363.1303,

found 363.1300.

3- (2-chlorophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1f):

1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.63,

158.20 (d, JC-F = 248.1 Hz), 144.66, 138.24, 133.96, 133.77 (d, JC-F = 50.8 Hz),

130.96, 130.83, 130.73, 129.48, 129.28, 128.86, 127.87, 127.03, 125.60, 124.87,

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117.26 (d, JC-F = 20.0 Hz), 116.95, 112.94, 33.92, 29.39; HRMS (EI-TOF):

m/zCalcd. for C22H17ClFN2O [M+H]+: 379.1008, found 379.1005.

3-(2-bromophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1g):

1H NMR (400MHz, CDCl3) 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, CDCl3) δ 172.56, 158.24 (d, JC-F = 248.5

Hz), 144.68, 139.97, 133.77 (d, JC-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, JC-F = 20.3 Hz), 116.95, 112.98,

34.06, 31.86; HRMS (EI-TOF): m/zCalcd. for C22H16BrFN2NaO [M+Na]+:

445.0322, found 445.0323.

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(2-(trifluoromethyl)phenyl)propanam

ide (1h): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.48, 158.15 (d, JC-F = 249.5 Hz),

144.67, 139.55, 133.76 (d, JC-F = 52.4 Hz), 132.15, 131.61, 131.00, 130.69, 129.25,

128.93, 128.77, 128.47, 126.73 (q, JC-F = 233 Hz ), 126.50,126.04 (q, JC-F = 5.7 Hz),

125.90, 123.18, 120.46, 117.31 (d, JC-F = 20.4 Hz), 117.02, 113.05, 36.00, 28.15;

HRMS (EI-TOF): m/zCalcd. for C23H17F4N2O [M+H]+: 413.1272, found 413.1275.

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N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-m-tolylpropanamide (1i): 1H NMR


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, CDCl3) δ 172.91, 158.17 (d, JC-F = 249.0 Hz), 144.79,

140.78, 138.16, 133.84 (d, JC-F = 46.7 Hz), 130.80, 129.35, 128.96, 128.47, 127.88,

127.01, 125.50, 117.28 (d, JC-F = 20.9 Hz), 116.98, 113.05, 36.19, 31.13, 21.43;

HRMS (EI-TOF): m/zCalcd. for C23H19FN2NaO [M+Na]+: 381.1374, found

381.1373.

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-methoxyphenyl)propanamide (1j):


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, CDCl3) δ 172.78, 159.77, 158.17 (d, JC-F =

248.5 Hz),144.78, 142.47, 133.82 (d, JC-F = 48.0 Hz), 130.80, 129.56, 128.95,

127.90, 125.60, 120.87, 117.32 (d, JC-F = 20.5 Hz), 117.00, 114.16, 113.05, 111.74,

55.26, 36.08, 31.28;HRMS (EI-TOF): m/zCalcd. for C23H19FN2NaO2 [M+Na]+:

397.1323, found 397.1327.

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N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-fluorophenyl)propanamide (1k): 1H

NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.51, 162.87 (d, JC-F = 244.1 Hz), 158.17 (d, JC-F =

246.1 Hz), 144.73, 143.39 (d, JC-F = 6.2 Hz), 133.84 (d, JC-F = 49.5 Hz), 131.00 (d,

JC-F = 6.8 Hz), 130.76,130.02 (d, JC-F = 8.3 Hz), 129.33, 128.96, 127.99, 125.69,

124.27, 117.34 (d, JC-F = 20.7 Hz), 116.99, 115.40 (d, JC-F = 20.9 Hz), 113.20 (d,

JC-F = 20.9 Hz), 35.70, 30.85; HRMS (EI-TOF): m/zCalcd. for C22H17F2N2O

[M+H]+: 363.1303, found 363.1307.

3-(3-chlorophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1l): 1H

NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.42, 158.11 (d, JC-F = 249.2 Hz), 144.65, 142.84, 134.21,

133.70 (d, JC-F = 53.3 Hz), 131.00 (d, JC-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, JC-F = 20.1 Hz), 116.97, 112.97,

35.66, 30.76; HRMS (EI-TOF): m/zCalcd. for C22H17ClFN2O [M+H]+: 379.1008,

found 379.1002.

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3-(3-bromophenyl)-N-(2-cyanophenyl)-N-(2-fluorophenyl)propanamide (1m):


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, CDCl3) δ 172.44, 158.11 (d,

JC-F = 248.4Hz), 144.72, 143.20, 133.86 (d, JC-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, JC-F = 19.0 Hz),

116.97, 113.06, 35.73, 30.80; HRMS (EI-TOF): m/zCalcd. for C22H16BrFN2NaO

[M+Na]+: 445.0322, found 445.0325.

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(3-(trifluoromethyl)phenyl)propanam

ide (1n): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.30,

158.15 (d, JC-F = 249.1 Hz), 144.60, 141.66, 133.81 (d, JC-F = 55.9 Hz), 132.10,

131.21, 130.98, 130.69, 130.60 (d, JC-F = 4 Hz), 130.26, 129.02, 128.84, 127.97,

125.67, 125.15 (q, JC-F = 4.0 Hz), 123.17 (d, JC-F = 3.0 Hz), 122.88, 120.17, 117.32

(d, JC-F = 19.8 Hz), 116.95, 112.94, 35.58, 30.84; HRMS (EI-TOF): m/zCalcd. for

C23H16F4N2NaO [M+Na]+: 435.1091, found 435.1095.

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N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(4-methoxyphenyl)propanamide (1o):

1H NMR (400 MHz, CDCl3) 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


157.91, 144.47, 133.59 (d, JC-F = 58.5 Hz), 132.60, 130.72 (d, JC-F = 7.2 Hz), 130.50,

129.22, 129.12, 128.63, 127.68, 125.41, 124.65, 117.15 (d, JC-F = 20.0 Hz), 116.83,

113.75, 112.71, 55.07, 36.18, 30.09; HRMS (EI-TOF): m/zCalcd. for C23H20FN2O2

[M+H]+: 375.1503, found 375.1503.

N-(2-cyanophenyl)-N-(2-fluorophenyl)-3-(4-fluorophenyl)propanamide (1p):1H

NMR (400 MHz, CDCl3) 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


158.18 (d, JC-F = 248.5 Hz), 144.72, 136.46, 133.59 (d, JC-F = 51.0 Hz), 130.90，19.3

Hz), 117.00, 115.29 (d, JC-F = 21.0 Hz), 113.11, 36.10, 30.30; HRMS (EI-TOF):

m/zCalcd. for C22H16F2N2NaO [M+Na]+: 385.1123, found 385.1124.

N-(2-cyanophenyl)-N,3-diphenylpropanamide (1q): 1H NMR (400 MHz, CDCl3)

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);

13C NMR (100 MHz, CDCl3) δ 172.90, 145.47, 141.58, 140.90, 133.98, 133.63,

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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 C22H18N2O [M+H]+: 327.1497, found

327.1495.

N-(2-cyanophenyl)-3-phenyl-N-o-tolylpropanamide (1r): 1H NMR (400 MHz,

CDCl3) 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, CDCl3) 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 C23H21N2O [M+H]+: 341.1654, found 341.1655.

1H NMR (400 MHz, CDCl3) 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, CDCl3) δ172.89, 158.23 (d, JC-F = 248.1 Hz),

144.76, 140.66, 133.82 (d, JC-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, JC-F = 20.4 Hz), 116.99,

113.05, 36.12, 31.07; HRMS (EI-TOF): m/zCalcd. for C22H13D5FN2O [M+H]+:

350.1717, found 350.1716.

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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.

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2.3 Optimization Studies

Table S1. Initial Screening Solventsa

Table S2. Screening of Temperaturea

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Table S3. Screening of Oxidantsa

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Table S4. Screening Equivalents of Oxidantsa

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Table S5. Screening of Additivesa

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Table S6.Screening of Timea

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Table S7.Screening of Templatesa

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Table S8.Screening of theequivalentsof ethyl acrylatea

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Table S9.Utilityof T3 with Palladium catalystsa

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*Cl2]2 (3.1 mg, 0.005 mmol), Cu

(CO2CF3)2·xH2O (28.9mg, 0.1 mmol), CF3CO2H (0.1 mmol), olefin (0.5 mmol) and

DCE (2.0 mL). The tube was evacuated then back-filled with O2 (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.

S21

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)phenyl)

acrylate (3amono): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.59, 167.14, 158.21 (d, JC-F = 251.0 Hz), 144.62, 142.93, 141.57,

134.74, 133.86 (d, JC-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, JC-F = 19.7 Hz), 116.99,


[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 (3adi): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.34, 166.87, 158.25 (d, JC-F = 166 Hz), 144.71, 143.75,

142.35, 135.497, 133.86 (d, JC-F = 52.2 Hz), 130.75, 130.61, 129.84, 128.92, 128.03,

125.69, 120.99, 119.97, 117.43 (d, JC-F = 13.1 Hz), 116.98, 113.06, 60.75, 35.67,

S22

30.84, 14.44; HRMS (EI-TOF): m/zCalcd. for C32H30FN2O5 [M+H]+: 541.2133,

found 541.2134.

(E)-ethyl-3-(3-(4-((2-cyanophenyl)(2-fluorophenyl)amino)-4-oxobutan-2-yl)phe

nyl)acrylate (3bmono): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.04,

167.10, 158.15 (d, JC-F = 254.6 Hz), 146.84, 144.75, 142.95, 134.71, 133.82 (d, JC-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 C28H26FN2O3 [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 (3bdi): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ

171.83, 166.86, 158.14 (d, JC-F = 251.1 Hz), 147.53, 144.56, 143.88, 135.44,

S23

133.85(d, JC-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

C33H31FN2NaO5 [M+Na]+: 577.2109, found 577.2108.

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-4-meth

ylphenyl)acrylate (3c): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.70, 167.27, 158.22 (d, JC-F = 246.8 Hz), 144.76, 144.56,

139.60, 139.00, 133.84 (d, JC-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, JC-F = 19.1 Hz),116.98, 113.08,


[M+H]+: 457.1922, found 457.1921.


oxyphenyl)acrylate (3d): 1H NMR (400 MHz, CDCl3) 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),

S24

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, CDCl3) δ 173.16, 167.49, 159.42, 158.22 (d,

JC-F = 240.7 Hz), 144.79, 144.39, 133.81 (d, JC-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,


[M+H]+: 473.1871, found 473.1871.

(E)-ethyl-3-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-4-fluor

ophenyl)acrylate (3e): 1H NMR (400 MHz, CDCl3) 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, CDCl3) 172.33, 167.00, 162.33 (d, JC-F = 249.2

Hz), 158.18 (d, JC-F = 247.4 Hz), 144.65, 143.45, 142.27 133.82 (d, JC-F = 52.6 Hz),

131.08, 131.03, 130.80 (d, JC-F = 3.6 Hz), 130.69, 129.28 (d, JC-F = 13.2 Hz), 128.89，

128.31(d, JC-F = 16.4 Hz), 127.94，125.68, 118.06, 117.33 (d, JC-F = 19.6 Hz),

116.94, 115.99 (d, JC-F = 22.7 Hz), 114.99 (d, JC-F = 22.4 Hz), 112.98, 60.58, 34.14,

24.82, 14.40; HRMS (EI-TOF): m/zCalcd. for C27H23F2N2O3 [M+H]+: 461.1671,

found 473.1670.

S25

(E)-ethyl-3-(4-chloro-3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropy

l)phenyl)acrylate (3f): 1H NMR (400 MHz, CDCl3) 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);

13C NMR (100 MHz, CDCl3) δ 172.38, 166.85, 158.24 (d, JC-F = 248.8 Hz), 144.70,

143.25,141.96，138.96, 135.88, 133.82 (d, JC-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, JC-F =

19.5 Hz), 116.95, 113.05, 60.66, 33.78, 29.36, 14.41; HRMS (EI-TOF): m/zCalcd.

for C27H23ClFN2O3 [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): 1H NMR (400 MHz, CDCl3) 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);

13C NMR (100 MHz, CDCl3) δ 172.18, 166.70, 158.24 (d, JC-F = 249.5 Hz), 144.51,

143.13, 141.82, 140.54, 133.66 (d, JC-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, JC-F =

19.5 Hz), 116.78, 112.85, 60.53, 33.73, 31.62, 14.24;HRMS (EI-TOF): m/zCalcd.

S26

for C27H23BrFN2O3 [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): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.19, 166.51, 158.16 (d, JC-F = 248.1 Hz), 144.65, 142.65, 140.29,

138.08, 135.89, 133.83 (d, JC-F = 56.8 Hz), 131.13, 130.63, 129.89, 129.59, 129.24,

128.84, 126.78 (q, JC-F = 248.1 Hz ), 126.42, 126.74 (q, JC-F = 5.6 Hz),

125.72,122.83, 121.02, 117.31 (d, JC-F = 19.8 Hz), 116.94, 112.99, 60.83, 35.84,

28.08, 14.36;HRMS (EI-TOF): m/zCalcd. for C28H23F4N2O3 [M+H]+: 511.1639,

found 511.1640.


ylphenyl)acrylate (3i): 1H NMR (400 MHz, CDCl3) 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,

S27

2 H), 2.31 (s, 3 H), 1.33 (t, J = 7.2 Hz, 3 H); 13

C NMR (100 MHz, CDCl3) δ 172.69,

167.23, 158.23 (d, JC-F = 250.4 Hz), 144.79, 141.48, 138.88, 134.71, 133.85 (d, JC-F

= 49.1 Hz), 133.61, 131.55, 130.93 (d, JC-F = 7.7 Hz), 130.79, 128.96, 127.96,

126.78, 125.66, 125.45, 119.33, 118.18, 117.36 (d, JC-F = 20.2 Hz), 117.00, 113.05,

60.57, 35.94, 30.93, 21.34, 14.45; HRMS (EI-TOF): m/zCalcd. for C28H23F4N2O3

[M+H]+:457.1922, found 457.1923.


oxyphenyl)acrylate (3j): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.55,

167.06, 160.15, 158.22 (d, JC-F = 249 Hz), 144.75, 144.57, 143.03, 135.97,133.85 (d,

JC-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, JC-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 C28H25FN2NaO4 [M+Na]+:

495.1691, found 495.1692.

S28


ophenyl)acrylate (3k): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.26, 166.79, 163.14 (d, JC-F =

245.1 Hz), 158.20 (d, JC-F = 251.0 Hz), 144.66, 143.98(d, JC-F = 7.9 Hz), 143.36,

136.73 (d, JC-F = 8.2 Hz), 133.88 (d, JC-F = 54.8 Hz), 131.10 (d, JC-F = 9.3 Hz)，

130.73, 129.26，128.92, 128.06, 125.79, 124.45 (d, JC-F = 2.1 Hz), 121.12, 119.75,

117.42 (d, JC-F = 20.8Hz), 117.32 (d, JC-F = 21.3 Hz), 116.99,113.05, 112.19 (d, JC-F

=22.0 Hz), 60.78, 35.47, 30.73, 14.43; HRMS (EI-TOF): m/zCalcd. for

C27H23F2N2O3 [M+H]+: 461.1671, found 461.1675.


ophenyl)acrylate (3l): 1H NMR (400 MHz, CDCl3) 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

S29

H), 1.33 (t, J = 7.2 Hz, 3 H); 13

C NMR (100 MHz, CDCl3) δ 172.24, 166.74, 158.19

(d, JC-F = 247.9 Hz), 144.66, 143.42, 143.10, 136.43, 134.93, 133.88 (d, JC-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, JC-F = 20.6 Hz), 116.99, 113.02, 60.79, 35.48, 30.66, 14.42;

HRMS (EI-TOF): m/zCalcd. for C27H23ClFN2O3 [M+H]+: 477.1376, found

477.1377.


ophenyl)acrylate (3m): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.18, 166.65, 158.18 (d, JC-F = 249.1 Hz),

144.66, 143.67, 142.94, 141.10, 136.71, 133.86 (d, JC-F = 53.7 Hz),133.13, 131.04,

130.71, 129.29 (d, JC-F = 13.7 Hz), 128.91，128.68, 128.02，127.17, 125.75, 123.08,

119.90, 117.41 (d, JC-F = 21.3 Hz), 116.95, 113.04, 60.76, 35.49, 30.64,

14.41;HRMS (EI-TOF): m/zCalcd. for C27H23BrFN2O3 [M+H]+: 521.0871, found

521.0870.

S30


ophenyl)acrylate (3n): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.11, 166.60, 158.21 (d, JC-F = 248.8 Hz), 144.66,

142.92, 142.69, 141.23, 135.63, 133.89 (d, JC-F = 55.2Hz), 132.17, 131.85, 131.56,

130.71, 128.90, 128.08, 126.77 (q, JC-F = 3.6 Hz), 125.80, 125.26, 122.64, 122.55,

120.38, 117.43 (d, JC-F = 20.5 Hz), 116.95, 113.06, 60.85, 35.43, 30.78, 14.42;

HRMS (EI-TOF): m/zCalcd. for C28H22F4N2NaO3 [M+Na]+: 533.1459, found

533.1460.


ophenyl)acrylate (3o): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.73,

167.66, 158.21 (d, JC-F = 253.5 Hz), 157.02, 144.74, 140.05, 138.67, 133.85 (d, JC-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, JC-F = 18.2 Hz), 116.99, 113.04, 111.39, 60.45, 55.69,


495.1691, found 495.1694.

S31


ophenyl)acrylate (3p): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ

172.40, 166.96, 160.14 (d, JC-F = 251.0 Hz), 158.22 (d, JC-F = 251.4 Hz), 144.69,

137.35, 137.00, 135.42, 133.87 (d, JC-F = 53.4 Hz), 131.88 (d, JC-F = 8.5 Hz),131.07,

130.73, 129.98, 129.33, 129.02 (d, JC-F = 2.9 Hz), 128.91, 128.01, 125.72, 122.56,

122.40 (d, JC-F = 11.8 Hz), 120.95 (d, JC-F = 6.6 Hz), 117.38 (d, JC-F = 18.4 Hz),

116.99, 116.26 (d, JC-F = 21.9 Hz), 113.04, 60.70, 35.88, 30.24, 14.43; HRMS

(EI-TOF): m/zCalcd. for C27H23F2N2O3 [M+H]+: 461.1671, found 461.1670.


ophenyl)acrylate (3q): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.55, 167.52, 160.12, 158.22 (d, JC-F =

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248.9 Hz), 144.88, 144.72, 143.05, 135.86, 133.85 (d, JC-F = 51.7 Hz), 130.96,

130.77, 129.31, 128.92, 127.98, 125.69, 121.07, 118.19, 117.38 (d, JC-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 C27H24FN2O4 [M+H]+: 459.1715, found 459.1716.


ophenyl)acrylate (3r): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.58, 167.19, 160.12, 158.21 (d, JC-F = 248.5 Hz),

144.70, 144.55, 143.01, 135.96, 133.85 (d, JC-F = 50.9 Hz), 131.03, 130.77, 128.93,

128.37, 127.97, 125.68, 121.09, 118.69, 117.37 (d, JC-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 C30H30FN2O3 [M+H]+: 485.2235, found 485.2234.


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ophenyl)acrylate (3s): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.58, 166.74, 160.06,

158.20 (d, JC-F = 249.1 Hz), 144.71, 142.85, 142.22, 137.81, 136.90, 133.82 (d,

JC-F= 53.5 Hz), 130.92, 130.73, 129.29, 128.87, 127.92, 125.65, 120.36, 117.93,

117.34 (d, JC-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 C28H27FN3O3 [M+H]+: 472.2031,

found 472.2031.


ophenyl)acrylate (3t): 1H NMR (400 MHz, CDCl3) 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,

CDCl3) δ201.12, 172.57, 160.15, 158.29 (d, JC-F = 264.5 Hz), 144.72, 143.08,

142.27, 136.11, 133.87 (d, JC-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, JC-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 C28H26FN2O3

[M+H]+: 457.1922, found 457.1921.

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ophenyl)acrylate (3u): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ193.88, 172.45,

160.23, 158.21 (d, JC-F = 248.4 Hz), 152.94, 144.70, 143.35, 135.48, 133.87 (d, JC-F

= 54.9 Hz), 131.00, 130.75, 129.31, 128.91, 128.02, 125.73, 121.67, 117.50,117.39

(d, JC-F = 21.8 Hz), 113.04, 111.17, 55.51, 35.70, 30.96; HRMS (EI-TOF): m/zCalcd.

for C26H22FN2O3 [M+H]+: 429.1609, found 429.1608.


ophenyl)acrylate (3v): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.64, 167.37, 159.89, 158.08 (d, JC-F =

249.3 Hz), 155.89, 144.76, 143.90, 142.67, 133.87 (d, JC-F = 47.5 Hz), 130.95,

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130.81, 128.97, 128.88, 127.98, 125.69, 119.47, 119.10, 117.37 (d, JC-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 C29H27FN2NaO4 [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): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ199.12,

172.65, 158.26 (d, JC-F = 250.0 Hz), 153.93, 144.76, 142.88, 141.25, 133.88 (d, JC-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, JC-F = 18.6 Hz), 116.97, 113.08, 36.08, 32.39,


479.1747, found 479.1748.

Dimethyl-2-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-meth

oxyphenyl)maleate (3x): 1H NMR (400 MHz, CDCl3) 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,

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3H),3.02 (t, J = 7.6 Hz, 2 H), 2.61 (t, J = 7.6 Hz, 2 H);13

C NMR (100 MHz, CDCl3)

δ172.64, 166.69, 165.58, 159.17,158.17 (d, JC-F = 249.2 Hz), 144.70, 143.66，

141.82，135.04, 133.75 (d, JC-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, JC-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

C29H25FN2NaO6 [M+Na]+: 539.1594, found 539.1590.

Dimethyl-2-(3-(3-((2-cyanophenyl)(2-fluorophenyl)amino)-3-oxopropyl)-5-methox

yphenyl)fumarate (3y):1H NMR (400 MHz, CDCl3) 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, CDCl3) δ172.37,

168.27, 165.44, 160.12,158.12 (d, JC-F = 248.8 Hz), 148.91, 144.61，143.29, 134.32

(d, JC-F = 52.0 Hz), 133.51, 130.98 (d, JC-F = 6.7 Hz),130.67, 129.92, 129.26 (d, JC-F

= 12.4 Hz), 128.85, 127.91, 125.65, 124.89, 119.35, 117.41, 117.07 (d, JC-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 C29H25FN2NaO6 [M+Na]+: 539.1594, found 539.1592.


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ophenyl)acrylate (3z): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.56, 160.13, 158.20 (d, JC-F = 249.0 Hz), 148.70,

144.71, 143.02, 136.47, 136.23, 133.85 (d, JC-F = 53.2 Hz), 130.73, 129.40,

128.90,127.97, 125.72, 120.56, 117.39 (d, JC-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 C29H31FN2O5P [M+H]+: 537.1949, found 537.1950.


ophenyl)acrylate (3α): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.81, 162.51 (d, JC-F =

245.8 Hz),160.17, 158.23 (d, JC-F = 247.1 Hz), 144.81, 142.76, 138.79, 133.86 (d,

JC-F = 49.1 Hz), 133.56, 133.53,130.86, 129.59, 129.41, 128.99, 128.43, 128.15 (d,

JC-F = 7.9 Hz), 127.97, 125.63, 121.71, 119.52, 117.36 (d, JC-F = 18.9 Hz), 117.04,

115.77 (d, JC-F = 21.6 Hz), 113.70, 113.09, 109.76, 55.43, 36.09, 31.37;H HRMS

(EI-TOF): m/zCalcd. for C31H25F2N2O2 [M+H]+: 495.1879, found 495.1881.

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ophenyl)acrylate (3β): 1H NMR (400 MHz, CDCl3) 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, CDCl3) δ 172.43, 160.21, 158.19 (d, JC-F = 248.4 Hz), 144.67, 143.36, 142.55,

140.79, 133.87 (d, JC-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, JC-F =

17.0 Hz), 116.99, 113.00, 111.60, 55.52, 35.64, 30.97; HRMS (EI-TOF): m/zCalcd.

for C31H26FN2O4S [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. 1H NMR (400 MHz, CDCl3) 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

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(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, CDCl3) 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 (7amono): 7 was olefinated following the general

procedure to provide 7amono and 7adi. 1H NMR (400 MHz, CDCl3) 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, CDCl3) 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.

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(2E,2'E)-diethyl-3,3'-(5-(3-(4-cyano-2,6-dimethylheptan-4-yl)-4-methoxy-N-met

hylphenylsulfonamido)-1,3-phenylene)diacrylate (7adi): 7 was olefinated

following the general procedure to provide 7amono and 7adi. 1H NMR (400 MHz,

CDCl3) 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, CDCl3) 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*Cl2]2 (3.1 mg, 0.005 mmol),

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Cu(CO2CF3)2•xH2O (28.9 mg, 0.1 mmol), CF3CO2H (0.1 mmol), olefin (0.5 mmol)

and DCE (2.0 mL). The tube was evacuated then back-filled with O2 (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 CH2Br2 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.

1 2 3 4 5

2

4

6

8

10

12

14

16

18

Yie

ld (

%)

Time (h)

Eq. 1

Eq. 2

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

1a-D

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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*Cl2]2 (0.31 g, 0.5 mmol), Cu (CO2CF3)2·xH2O (2.89 g, 10 mmol),

CF3CO2H (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 O2 (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 MgSO4, 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).

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3. NMR Spectra for New Compounds

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1H NMR of 3e at room temperature used d

6-DMSO as solvent

1H NMR of 3e at 100℃d

6-DMSO as solvent

Coordination Chemistry Institute, State Key Laboratory … Xu,† Yi Lu,*, ... ‡ Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California

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