Supporting Information for. Rhodium-Catalyzed β-selective Oxidative Heck-Type

Supporting Information for Rhodium-Catalyzed β-selective Oxidative Heck-Type Coupling of Vinyl Acetate via C-H Activation Hui-Jun Zhang,* Weidong Lin, Feng Su, and Ting-Bin Wen* Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R. China. Contents: 1) General Information S2 2) Reaction Optimization S2-S3 3) Procedures and Characterization Data S3-S12 4) References S12 5) 1 H, 13 C, and 19 F NMR Spectra S13-S52 S1

1) General Information All commercial reagents were used without further purification. 1 H, 13 C, and 19 F NMR spectra were recorded at 500 MHz, 600 MHz, or 400 MHz in DMSO-d 6, acetone-d 6, CD 3CN, or CDCl 3 as solvent. Chemical shifts are given in ppm with reference to the residual solvent resonance of the deuterated solvents. High-resolution mass spectra were recorded on a FT-MS instrument using ESI technique. 2) Reaction Optimization a entry R [M] (mol %) [Ag] (mol %) or oxidant (equiv) solvent T ( o C) yield (%) b additive (equiv) 3 4 1 Ac [Cp*Rh(MeCN) 3](SbF 6) - Cu(OAc) 2 (2.1) t-amoh 120 (22) - (5) 2 Ac [Cp*Rh(MeCN) 3](SbF 6) - Cu(OAc) 2 (2.1) t-amoh 80 (28) - (5) 3 Ac [Cp*Rh(MeCN) 3](SbF 6) - Cu(OAc) 2 (2.1) t-amoh 50 (14) - (5) 4 Ac [Cp*Rh(MeCN) 3](SbF 6) KOAc (2) Cu(OAc) 2 (2.1) t-amoh 120 0 0 (5) 5 Ac [Cp*RhCl2]2 (2.5) - Cu(OAc) 2 (2.1) t-amoh 120 0 0 6 Ac [Rh(cod)Cl]2 (5) - Cu(OAc) 2 (2.1) t-amoh 120 0 0 7 Ac RhCl(PPh3)3 (5) - Cu(OAc) 2 (2.1) t-amoh 120 0 0 8 Ac Pd(OAc)2 (10) Cu(OAc) 2 (2.1) t-amoh 120 0 0 9 Ac [RuCl2(p-cymene)]2 (5) Cu(OAc) 2 (2.1) t-amoh 120 0 0 10 Ac [Cp*Rh(MeCN) 3](SbF 6) Cu(OAc) 2 (2.1) Toluene 120 (14) - (5) 11 Ac [Cp*Rh(MeCN) 3](SbF 6) Cu(OAc) 2 (2.1) 1,4-dioxane 120 (23) - (5) 12 Ac [Cp*Rh(MeCN) 3](SbF 6) Cu(OAc) 2 (2.1) DMF 120 0 0 (5) 13 Ac [Cp*Rh(MeCN) 3](SbF 6) Cu(OAc) 2 (2.1) DCE 120 (20) - (5) 14 Ac [Cp*Rh(MeCN) 3](SbF 6) Cu(OAc) 2 (2.1) THF 120 (31) - (5) 15 Ac [Cp*Rh(MeCN) 3](SbF 6) Cu(OAc) 2 (2.1) DME 80 (38) - (5) 16 Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) Cu(OAc) 2 (2.1) DME 80 (36) - 17 c Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) Cu(OAc) 2 (2.1) DME 80 (38) 18 Ac [Cp*Rh(MeCN) 3](SbF 6) - AgOAc (2.0) t-amoh 120 (15) - (5) 19 Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) CuO (2.1) DME 80 (15) - 20 Ac [Cp*Rh(MeCN) 3](SbF 6) - CuCl2 (2.1) DME 80 0 0 (5) 21 Ac [Cp*RhCl 2] 2 (2.5) AgOTf (30) Cu(OAc) 2 (2.1) DME 80 (37) - 22 Ac [Cp*RhCl 2] 2 (2.5) AgPF6 (30) Cu(OAc) 2 (2.1) DME 80 (21) - S2

23 Ac [Cp*RhCl 2] 2 (2.5) AgTFA (30) Cu(OAc) 2 (2.1) DME 80 trace - 24 c Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) Cu(OAc) 2 (2.1) DME 80 (43) - HOAc (2) 25 c Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) Cu(OAc) 2 (2.1) acetone 80 47 10 26 c Piv [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) Cu(OAc) 2 (2.1) acetone 80 45 11 27 c,d Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (30) Cu(OAc) 2 (2.1) acetone 80 49 10 28 c Ac [Cp*RhCl 2] 2 (2.5) AgBF4 (30) Cu(OAc) 2 (2.1) acetone 80 48 15 29 c Ac [Cp*RhCl 2] 2 (2.5) AgBF4 (15) Cu(OAc) 2 (2.1) acetone 80 57 14 30 c Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (20) Cu(OAc) 2 (2.1) acetone 80 55 15 31 c Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (20) Cu(OAc) 2 (1.2) acetone 80 55 22 32 c Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (10) Cu(OAc) 2 (2.1) acetone 80 62 14 33 c Ac [Cp*RhCl 2] 2 (5) AgSbF 6 (20) Cu(OAc) 2 (1.1) acetone 80 66 18 34 c,e Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (10) Cu(OAc) 2 (1.1) acetone 80 66 24 35 c,e Ac [Cp*RhCl 2] 2 (2.5) AgSbF 6 (10) Cu(OAc) 2 (1.1) - 80 43 31 36 c,e Py [Cp*RhCl 2] 2 (2.5) AgSbF 6 (10) Cu(OAc) 2 (0.3) acetone 80 trace - a Reaction conditions: 1 (0.2 mmol), 2 (1.0 mmol), [M], [Ag], oxidant, solvent (1.5 ml), Ar, 12 h. b Isolated yield. Value in parentheses indicates NMR yield using CH 2Br 2 as internal standard. c In air. d 12 h. e Vinyl acetate (10 equiv). entry oxidant (equiv) additive (equiv) solvent (ml) T ( o C) yield (%) b 1 c Cu(OAc) 2 (1.1) - acetone (1.5) 80 66 2 c Cu(OAc) 2 (1.1) - acetone (1.5) 100 56 3 Cu(OAc) 2 (1.1) - acetone (1.5) 80 70 4 d Cu(OAc) 2 (1.1) - acetone (1.5) 80 64 5 Cu(OAc) 2 (1.1) - acetone (0.8) 80 73 6 c Cu(OAc) 2 (1.1) - - 80 62 7 Cu(OAc) 2 (1.1) - VA (1.0) 80 74 8 Cu(OAc) 2 (0.3) - acetone (0.8) 80 85 9 Cu(OAc) 2 (0.3) PivOH (2) acetone (0.8) 80 57 10 - - acetone (0.8) 80 56 11 - - DME (0.8) 80 34 12 - HOAc (1) acetone (0.8) 80 52 13 - H 2O (2) acetone (0.8) 80 24 14 e - - acetone (0.8) 80 36 a Reaction conditions: 1 (0.2 mmol), 2a (2.0 mmol), [M], [Ag], oxidant, solvent, air, 24 h. b Isolated yield. c 5 equiv of 2a. d 6 h. e Under O 2 atmosphere. 3) Procedures and Characterization Data General Procedures for the Olefination of Acetanilides with Vinyl Esters. To a 15 ml Schlenk tube, acetanilide 1 (0.2 mmol), vinyl ester 2 (2.0 mmol), [Cp*RhCl 2] 2 (2.5 mol %), AgSbF 6 (10 mol %), Cu(OAc) 2 H 2O (30 mol %), and acetone (0.8 ml) were added under air. Then the tube was sealed with a Teflon lined cap, and the mixture was stirred at 80 o C for 24 h. Subsequently, the reaction mixture was concentrated under vacuum. The residue was purified by column chromatography to afford the product 3 (PE:EA = 3:1-1:2). S3

General Procedures for the One-Pot Systhesis of Indole Derivatives. To a 15 ml Schlenk tube, acetanilide 1 (0.2 mmol), vinyl acetate 2 (2.0 mmol), [Cp*RhCl 2] 2 (2.5 mol %), AgSbF 6 (10 mol %), Cu(OAc) 2 H 2O (30 mol %), and acetone (0.8 ml) were added under air. The tube was sealed with a Teflon lined cap, and the mixture was stirred at 80 o C for 24 h. After cooling the reaction mixture to rt, the solvent was removed under vacuum. Then, 6 M HCl (0.1 ml)/thf (0.4 ml) or 80 % hydrazine hydrate (0.5 ml) was added and the reaction mixture was stirred at rt for 6 h. Subsequetnly, the resulting mixture was diluted with DCM and washed with sat. NaHCO 3 solution. The organic layer was collected and concentrated. The residue was purified by column chromatography to afford the product 5 or 6 (PE:EA = 10:1-2:1). (E)-2-Acetamido-4-methylstyryl acetate (3aa): white solid; mp 167-168 o C; yield 85% (39.6 mg); 1 H NMR (500 MHz, DMSO) δ 9.44 (s, 1H), 7.70 (d, J = 12.7 Hz, 1H), 7.42 (d, J = 7.9 Hz, 1H), 7.23 (s, 1H), 6.96 (d, J = 7.8 Hz, 1H), 6.55 (d, J = 12.7 Hz, 1H), 2.26 (s, 3H), 2.19 (s, 3H), 2.05 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.5, 167.8, 137.0, 136.4, 135.2, 126.6, 126.3, 125.5, 125.2, 111.2, 23.2, 20.7, 20.4; HRMS m/z (ESI) calcd. for C 13H 15NNaO + 3 (M+Na) + 256.0944, found 256.0941. (E)-4-Methyl-2-pivalamidostyryl acetate (3ba): white solid; mp 94-95 o C; yield 70% (38.5 mg); 1 H NMR (500 MHz, acetone) δ 8.29 (s, 1H), 7.69 (d, J = 12.8 Hz, 1H), 7.36 (d, J = 7.9 Hz, 1H), 7.24 (s, 1H), 6.99 (d, J = 7.9 Hz, 1H), 6.44 (d, J = 12.8 Hz, 1H), 2.29 (s, 3H), 2.16 (s, 3H), 1.32 (s, 9H); 13 C NMR (126 MHz, acetone) δ 177.3, 168.5, 138.2, 137.5, 136.5, 128.2, 127.51, 127.45, 126.7, 111.8, 39.9, 27.9, 21.1, 20.6; HRMS m/z (ESI) calcd. for C 16H 21NNaO + 3 (M+Na) + 298.1414, found 298.1409. (E)-2-Acetamido-4-methoxystyryl acetate (3ea): white solid; mp 127-128 o C; yield 77% (38.4 mg); 1 H NMR (500 MHz, CD 3CN) δ 8.14 (s, 1H), 7.59 (d, J = 12.6 Hz, 1H), 7.35 (d, J = 8.5 Hz, 1H), 7.12 (s, 1H), 6.71 (d, J = 8.2 Hz, 1H), 6.44 (d, J = 12.7 Hz, 1H), 3.74 (s, 3H), 2.39 (s, 3H), 2.07 (s, 3H); 13 C NMR (126 MHz, CD 3CN) δ 170.3, 169.2, 160.3, 137.4, 137.3, 128.1, 121.5, 112.6, 111.80, 111.76, 56.0, 23.9, 21.0; HRMS m/z (ESI) calcd. for C 13H 15NNaO + 4 (M+Na) + 272.0893, found 272.0891. S4

(E)-3-Acetamido-4-(2-acetoxyvinyl)phenyl acetate (3fa): white solid; mp 157-158 o C; yield 65% (36.2 mg); 1 H NMR (500 MHz, DMSO) δ 9.54 (s, 1H), 7.72 (d, J = 12.7 Hz, 1H), 7.55 (d, J = 8.5 Hz, 1H), 7.31 (s, 1H), 6.91 (dd, J = 8.3, 1.5 Hz, 1H), 6.60 (d, J = 12.6 Hz, 1H), 2.25 (s, 3H), 2.20 (s, 3H), 2.07 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 169.1, 168.7, 167.9, 149.6, 137.2, 136.2, 126.6, 124.9, 118.9, 118.6, 110.6, 23.4, 20.8, 20.5; HRMS m/z (ESI) calcd. for C 14H 15NNaO + 5 (M+Na) + 300.0842, found 300.0839. (E)-2-Acetamido-4-(N-(methylsulfonyl)methylsulfonamido)styryl acetate (3ga): white solid; mp 211-212 o C; yield 85% (66.7 mg); 1 H NMR (600 MHz, DMSO) δ 9.66 (s, 1H), 7.85 (d, J = 12.6 Hz, 1H), 7.66 (d, J = 8.1 Hz, 1H), 7.59 (s, 1H), 7.29 (d, J = 7.6 Hz, 1H), 6.61 (d, J = 12.6 Hz, 1H), 3.37 (s, 6H), 2.22 (s, 3H), 2.09 (s, 3H); 13 C NMR (101 MHz, DMSO) δ 168.8, 167.8, 138.4, 135.9, 132.5, 129.7, 127.81, 127.77, 126.6, 110.3, 42.9, 23.3, 20.5; HRMS m/z (ESI) calcd. for C 14H 18N 2NaO 7S + 2 (M+Na) + 413.0448, found 413.0443. (E)-2-Acetamido-4-(acetamidomethyl)styryl acetate (3ha): white solid; mp 213-214 o C; yield 94% (54.3 mg); 1 H NMR (500 MHz, DMSO) δ 9.49 (s, 1H), 8.35 (t, J = 5.9 Hz, 1H), 7.71 (d, J = 12.7 Hz, 1H), 7.49 (d, J = 8.0 Hz, 1H), 7.26 (s, 1H), 7.03 (d, J = 7.9 Hz, 1H), 6.52 (d, J = 12.7 Hz, 1H), 4.20 (d, J = 5.9 Hz, 2H), 2.19 (s, 3H), 2.05 (s, 3H), 1.86 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 169.2, 168.6, 167.9, 139.3, 136.7, 135.3, 126.7, 125.6, 125.1, 124.7, 111.2, 41.7, 23.2, 22.6, 20.5; HRMS m/z (ESI) calcd. for C 15H 18N 2NaO + 4 (M+Na) + 313.1159, found 313.1155. (E)-2-Acetamido-4-chlorostyryl acetate (3ia): white solid; mp 168-169 o C; yield 63% (31.9 mg); 1 H NMR (500 MHz, acetone) δ 8.84 (s, 1H), 7.89 (s, 1H), 7.71 (d, J = 12.6 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 7.14 (d, J = 10.1 Hz, 1H), 6.58 (d, J = 12.6 Hz, 1H), 2.18 (s, 3H), 2.15 (s, 3H); 13 C NMR (126 MHz, acetone) δ 169.4, 168.3, 138.9, 137.9, 133.3, 128.4, 126.5, 125.6, 124.9, 110.7, 23.9, 20.5; HRMS m/z (ESI) calcd. for C 12H 12ClNNaO + 3 (M+Na) + 276.0398, found 276.0395. (E)-2-Acetamido-4-bromostyryl acetate (3ja): white solid; mp 160-161 o C; yield 62% (36.9 mg); 1 H NMR (500 MHz, DMSO) δ 9.59 (s, 1H), S5

7.76 (d, J = 12.7 Hz, 1H), 7.71 (d, J = 1.6 Hz, 1H), 7.50 (d, J = 8.4 Hz, 1H), 7.30 (dd, J = 8.4, 1.8 Hz, 1H), 6.56 (d, J = 12.7 Hz, 1H), 2.20 (s, 3H), 2.07 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.9, 167.8, 137.7, 136.7, 128.0, 128.0, 127.6, 126.8, 119.8, 110.3, 23.3, 20.5; HRMS m/z (ESI) calcd. for C 12H 12BrNNaO + 3 (M+Na) + 319.9893, found 319.9888. (E)-2-Acetamido-4-(trifluoromethyl)styryl acetate (3ka): white solid; mp 173-174 o C; yield 59% (33.9 mg); 1 H NMR (500 MHz, acetone) δ 8.96 (s, 1H), 8.17 (s, 1H), 7.83 (d, J = 12.7 Hz, 1H), 7.70 (d, J = 8.2 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 6.66 (d, J = 12.7 Hz, 1H), 2.20 (s, 3H), 2.18 (s, 3H); 13 C NMR (126 MHz, acetone) δ 169.6, 168.3, 140.1, 137.3, 131.9, 129.8 (q, J = 32.3 Hz), 127.9, 125.2 (q, J = 271.3 Hz), 122.0, 110.6, 23.9, 20.5; 19 F NMR (376 MHz, Acetone) δ -63.1; HRMS m/z (ESI) calcd. for C 13H 12F 3NNaO + 3 (M+Na) + 310.0661, found 310.0659. Methyl (E)-3-acetamido-4-(2-acetoxyvinyl)benzoate (3la): white solid; mp 172-173 o C; yield 91% (50.5 mg); 1 H NMR (500 MHz, acetone) δ 8.91 (s, 1H), 8.31 (s, 1H), 7.84 (d, J = 12.7 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 6.64 (d, J = 12.7 Hz, 1H), 3.87 (s, 3H), 2.19 (s, 3H), 2.17 (s, 3H); 13 C NMR (126 MHz, acetone) δ 169.5, 168.3, 166.8, 139.8, 136.7, 133.4, 130.2, 127.2, 126.9, 126.8, 111.0, 52.4, 23.7, 20.5; HRMS m/z (ESI) calcd. for C 14H 15NNaO + 5 (M+Na) + 300.0842, found 300.0840. (E)-2-Acetamido-4-nitrostyryl acetate (3ma): yellow solid; mp 190-191 o C; yield 59% (31.1 mg); 1 H NMR (500 MHz, DMSO) δ 9.79 (s, 1H), 8.45 (d, J = 2.2 Hz, 1H), 7.96 (d, J = 12.7 Hz, 1H), 7.94 (dd, J = 8.7, 2.4 Hz, 1H), 7.84 (d, J = 8.7 Hz, 1H), 6.71 (d, J = 12.6 Hz, 1H), 2.23 (s, 3H), 2.13 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 169.2, 167.6, 146.1, 140.2, 135.9, 134.1, 126.7, 119.7, 119.6, 109.7, 23.4, 20.4; HRMS m/z (ESI) calcd. for C 12H 12N 2NaO + 5 (M+Na) + 287.0638, found 287.0636. (E)-2-Acetamido-3-methylstyryl acetate (3na): white solid; mp 139-140 o C; yield 75% (34.8 mg); 1 H NMR (500 MHz, DMSO) δ 9.35 (s, 1H), 7.74 (d, J = 12.8 Hz, 1H), 7.40 (dd, J = 6.2, 3.1 Hz, 1H), 7.15 (s, 1H), 7.14 (d, J = 3.4 Hz, 1H), 6.44 (d, J = 12.8 Hz, 1H), 2.19 (s, 3H), 2.13 (s, 3H), 2.06 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.3, 167.9, 137.0, 136.2, 134.2, 131.4, 129.3, 126.8, 123.1, 111.8, 22.5, 20.5, 18.1; S6

HRMS m/z (ESI) calcd. for C 13H 15NNaO + 3 (M+Na) + 256.0944, found 256.0942. (E)-2-Acetamido-3-bromostyryl acetate (3oa): white solid; mp 174-175 o C; yield 16% (9.6 mg); 1 H NMR (500 MHz, acetone) δ 8.78 (s, 1H), 7.81 (d, J = 12.8 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.19 (t, J = 7.9 Hz, 1H), 6.50 (d, J = 12.8 Hz, 1H), 2.17 (s, 3H), 2.15 (s, 3H); 13 C NMR (126 MHz, acetone) δ 169.2, 168.4, 138.9, 136.1, 135.3, 132.3, 129.5, 125.8, 124.9, 112.2, 22.9, 20.5; HRMS m/z (ESI) calcd. for C 12H 12BrNNaO + 3 (M+Na) + 319.9893, found 319.9889. (E)-2-Acetamidostyryl acetate (3pa): white solid; mp 148-149 o C; yield 47% (20.6 mg); 1 H NMR (500 MHz, DMSO) δ 9.49 (s, 1H), 7.73 (d, J = 12.7 Hz, 1H), 7.53 (d, J = 7.5 Hz, 1H), 7.41 (d, J = 7.8 Hz, 1H), 7.24 (t, J = 7.4 Hz, 1H), 7.14 (t, J = 7.3 Hz, 1H), 6.58 (d, J = 12.7 Hz, 1H), 2.20 (s, 3H), 2.06 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.5, 167.9, 137.0, 135.3, 128.1, 127.6, 126.2, 125.7, 125.5, 111.3, 23.2, 20.4; HRMS m/z (ESI) calcd. for C 12H 13NNaO + 3 (M+Na) + 242.0788, found 242.0785. (1E,1'E)-(2-Acetamido-1,3-phenylene)bis(ethene-2,1-diyl) diacetate (4pa): white solid; mp 183-184 o C; yield 42% (25.5 mg); 1 H NMR (500 MHz, DMSO) δ 9.47 (s, 1H), 7.76 (d, J = 12.8 Hz, 2H), 7.50 (d, J = 7.8 Hz, 2H), 7.22 (t, J = 7.8 Hz, 1H), 6.40 (d, J = 12.8 Hz, 2H), 2.19 (s, 6H), 2.07 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.7, 167.9, 137.4, 132.9, 132.3, 127.3, 124.7, 111.4, 22.6, 20.5; HRMS m/z (ESI) calcd. for C 16H 17NNaO + 5 (M+Na) + 326.0999, found 326.0995. (E)-2-Acetamido-5-methylstyryl acetate (3qa): white solid; mp 162-163 o C; yield 47% (21.9 mg); 1 H NMR (500 MHz, DMSO) δ 9.41 (s, 1H), 7.74 (d, J = 12.8 Hz, 1H), 7.36 (s, 1H), 7.25 (d, J = 8.1 Hz, 1H), 7.04 (d, J = 7.9 Hz, 1H), 6.53 (d, J = 12.7 Hz, 1H), 2.28 (s, 3H), 2.20 (s, 3H), 2.04 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.5, 167.9, 136.8, 134.8, 132.8, 128.3, 128.0, 126.3, 125.9, 111.3, 23.1, 20.5; HRMS m/z (ESI) calcd. for C 13H 15NNaO + 3 (M+Na) + 256.0944, found 256.0942. (1E,1'E)-(2-Acetamido-5-methyl-1,3-phenylene)bis(ethene-2,1-diyl) diacetate (4qa): white solid; mp 229-230 o C; yield 36% (22.8 mg); 1 H NMR (500 MHz, DMSO) δ 9.37 (s, 1H), 7.76 (d, J = 12.7 Hz, 2H), 7.33 (s, 2H), 6.37 (d, J = 12.7 Hz, 2H), 2.30 (s, 3H), 2.19 (s, 6H), 2.06 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.8, 167.9, 137.2, 136.6, 132.0, 130.5, 125.2, 111.5, S7

22.6, 20.50, 20.46; HRMS m/z (ESI) calcd. for C 17H 19NNaO + 5 (M+Na) + 340.1155, found 340.1151. (E)-2-Acetamido-5-bromostyryl acetate (3ra): white solid; mp 204-205 o C; yield 54% (32.2 mg); 1 H NMR (500 MHz, acetone) δ 8.80 (s, 1H), 7.77 (d, J = 12.7 Hz, 1H), 7.66 (d, J = 9.5 Hz, 2H), 7.39 (dd, J = 8.6, 2.0 Hz, 1H), 6.56 (d, J = 12.7 Hz, 1H), 2.18 (s, 3H), 2.13 (s, 3H); 13 C NMR (126 MHz, acetone) δ 169.2, 168.3, 139.4, 136.1, 131.2, 130.7, 129.6, 127.6, 118.3, 110.6, 23.8, 20.5; HRMS m/z (ESI) calcd. for C 12H 12BrNNaO + 3 (M+Na) + 319.9893, found 319.9890. (1E,1'E)-(2-acetamido-5-bromo-1,3-phenylene)bis(ethene-2,1-diyl) diacetate (4ra): white solid; mp 219-220 o C; yield 30% (22.9 mg); 1 H NMR (500 MHz, DMSO) δ 9.50 (s, 1H), 7.86 (d, J = 12.8 Hz, 2H), 7.72 (s, 2H), 6.34 (d, J = 12.8 Hz, 2H), 2.19 (s, 6H), 2.07 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.8, 167.7, 138.8, 134.7, 132.1, 126.9, 120.4, 110.3, 22.6, 20.4; HRMS m/z (ESI) calcd. for C 16H 16BrNNaO + 5 (M+Na) + 404.0104, found 404.0100. (E)-2-Pivalamidostyryl acetate (3sa): white solid; mp 89-90 o C; yield 43% (22.3 mg); 1 H NMR (500 MHz, acetone) δ 8.34 (s, 1H), 7.73 (d, J = 12.8 Hz, 1H), 7.48 (dd, J = 7.7, 1.5 Hz, 1H), 7.42 (dd, J = 7.9, 1.1 Hz, 1H), 7.23 (td, J = 7.7, 1.5 Hz, 1H), 7.16 (td, J = 7.6, 1.2 Hz, 1H), 6.49 (d, J = 12.8 Hz, 1H), 2.17 (s, 3H), 1.32 (s, 9H); 13 C NMR (126 MHz, acetone) δ 177.4, 168.5, 138.3, 136.8, 130.4, 128.4, 127.6, 127.1, 126.6, 112.0, 39.9, 27.9, 20.6; HRMS m/z (ESI) calcd. for C 15H 19NNaO + 3 (M+Na) + 284.1257, found 284.1253. (1E,1'E)-(2-Pivalamido-1,3-phenylene)bis(ethene-2,1-diyl) diacetate (4sa): white solid; mp 144-145 o C; yield 21% (14.4 mg); 1 H NMR (500 MHz, DMSO) δ 9.10 (s, 1H), 7.76 (d, J = 12.8 Hz, 2H), 7.51 (d, J = 7.8 Hz, 2H), 7.24 (t, J = 7.8 Hz, 1H), 6.33 (d, J = 12.8 Hz, 2H), 2.19 (s, 6H), 1.26 (s, 9H); 13 C NMR (126 MHz, DMSO) δ 176.7, 167.8, 137.4, 133.2, 132.9, 127.3, 124.8, 111.1, 38.6, 27.3, 20.4; HRMS m/z (ESI) calcd. for C 19H 23NNaO + 5 (M+Na) + 368.1468, found 368.1463. (E)-2-(1-Acetamidonaphthalen-2-yl)vinyl acetate (3ta): white solid; mp 212-213 o C; yield 66% (35.3 mg); 1 H NMR (500 MHz, DMSO) δ 9.78 (s, 1H), 7.97 (d, J = 12.8 Hz, 1H), 7.91 (d, J = 7.5 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.83 (d, J = 8.8 Hz, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.55 7.48 (m, 2H), 6.61 (d, J = 12.8 S8

Hz, 1H), 2.22 (s, 3H), 2.20 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 169.3, 167.9, 137.9, 133.0, 131.0, 130.8, 128.5, 127.9, 127.2, 126.7, 126.0, 123.7, 122.9, 111.8, 22.7, 20.5; HRMS m/z (ESI) calcd. for C 16H 15NNaO + 3 (M+Na) + 292.0944, found 292.0941. (E)-2-(2-acetamidonaphthalen-1-yl)vinyl acetate (3ua): white solid; mp 204-205 o C; yield 75% (40.5 mg); 1 H NMR (500 MHz, DMSO) δ 9.64 (s, 1H), 8.10 (s, 1H), 7.99 (s, 1H), 7.91 7.85 (m, 2H), 7.83 7.78 (m, 1H), 7.45 (p, J = 6.3 Hz, 2H), 6.75 (d, J = 12.6 Hz, 1H), 2.23 (s, 3H), 2.13 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.9, 167.9, 137.5, 133.5, 132.5, 130.9, 127.9, 127.5, 127.1, 126.2, 125.7, 124.7, 123.2, 111.4, 23.4, 20.5; HRMS m/z (ESI) calcd. for C 16H 15NNaO + 3 (M+Na) + 292.0944, found 292.0941. (E)-2-(1-Acetylindolin-7-yl)vinyl acetate (3va): white solid; mp 105-106 o C; yield 63% (31.1 mg); 1 H NMR (500 MHz, DMSO) δ 7.59 (d, J = 12.8 Hz, 1H), 7.31 (d, J = 7.8 Hz, 1H), 7.18 (d, J = 7.2 Hz, 1H), 7.06 (t, J = 7.6 Hz, 1H), 6.49 (d, J = 12.8 Hz, 1H), 4.06 (t, J = 7.6 Hz, 2H), 2.98 (t, J = 7.5 Hz, 2H), 2.20 (s, 3H), 2.17 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.6, 168.0, 140.4, 135.8, 135.5, 125.2, 124.2, 124.1, 123.6, 114.4, 50.8, 29.1, 23.8, 20.5; HRMS m/z (ESI) calcd. for C 14H 15NNaO + 3 (M+Na) + 268.0944, found 268.0940. (E)-2-Acetamido-4-methylstyryl butyrate (3ab): white solid; mp 126-127 o C; yield 89% (46.4 mg); 1 H NMR (500 MHz, DMSO) δ 9.43 (s, 1H), 7.71 (d, J = 12.7 Hz, 1H), 7.42 (d, J = 7.9 Hz, 1H), 7.22 (s, 1H), 6.96 (d, J = 7.8 Hz, 1H), 6.53 (d, J = 12.7 Hz, 1H), 2.47 (t, J = 7.2 Hz, 2H), 2.26 (s, 3H), 2.04 (s, 3H), 1.61 (h, J = 7.3 Hz, 2H), 0.93 (t, J = 7.4 Hz, 3H); 13 C NMR (126 MHz, DMSO) δ 170.3, 168.4, 137.0, 136.3, 135.1, 126.6, 126.3, 125.5, 125.1, 111.2, 34.9, 23.2, 20.6, 17.6, 13.3; HRMS m/z (ESI) calcd. for C 15H 19NNaO + 3 (M+Na) + 284.1257, found 284.1252. (E)-2-Acetamido-4-methylstyryl pivalate (3ac): white solid; mp 146-147 o C; yield 66% (36.4 mg); 1 H NMR (500 MHz, acetone) δ 8.74 (s, 1H), 7.69 (d, J = 12.7 Hz, 1H), 7.46 (s, 1H), 7.36 (d, J = 7.9 Hz, 1H), 6.96 (d, J = 7.7 Hz, 1H), 6.61 (d, J = 12.7 Hz, 1H), 2.29 (s, 3H), 2.11 (s, 3H), 1.26 (s, 9H); 13 C NMR (126 MHz, acetone) δ 175.8, 169.2, 138.3, 138.0, 136.5, 127.0, 126.9, 126.7, 125.9, 111.8, 39.3, 27.2, 23.7, 21.2; HRMS m/z (ESI) calcd. for C 16H 21NNaO + 3 (M+Na) + 298.1414, found 298.1408. S9

(E)-2-Acetamido-4-methylstyryl octanoate (3ad): white solid; mp 143-144 o C; yield 69% (44.1 mg); 1 H NMR (500 MHz, acetone) δ 8.71 (s, 1H), 7.70 (d, J = 12.7 Hz, 1H), 7.47 (s, 1H), 7.36 (d, J = 7.9 Hz, 1H), 6.96 (d, J = 7.7 Hz, 1H), 6.56 (d, J = 12.7 Hz, 1H), 2.47 (t, J = 7.4 Hz, 2H), 2.29 (s, 3H), 2.12 (s, 3H), 1.69 1.63 (m, 2H), 1.39 1.33 (m, 4H), 1.31 1.28 (m, 4H), 0.89 (t, J = 6.6 Hz, 3H); 13 C NMR (126 MHz, acetone) δ 171.2, 169.2, 138.3, 137.6, 136.5, 126.9, 126.8, 126.7, 125.9, 111.8, 34.2, 32.4, 29.7, 29.6, 25.3, 23.7, 23.2, 21.2, 14.3; HRMS m/z (ESI) calcd. for C 19H 27NNaO + 3 (M+Na) + 340.1883, found 340.1878. (E)-2-Acetamido-4-methylstyryl benzoate (3ae): white solid; mp 199-200 o C; yield 90% (53.1 mg); 1 H NMR (500 MHz, DMSO) δ 9.50 (s, 1H), 8.10 (d, J = 7.3 Hz, 2H), 7.95 (d, J = 12.6 Hz, 1H), 7.74 (t, J = 7.4 Hz, 1H), 7.61 (t, J = 7.7 Hz, 2H), 7.51 (d, J = 7.9 Hz, 1H), 7.26 (s, 1H), 7.00 (d, J = 7.8 Hz, 1H), 6.77 (d, J = 12.6 Hz, 1H), 2.28 (s, 3H), 2.08 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.5, 163.1, 137.2, 136.6, 135.3, 134.1, 129.6, 129.0, 128.2, 126.7, 126.4, 125.7, 125.1, 112.3, 23.2, 20.7; HRMS m/z (ESI) calcd. for C 18H 17NNaO + 3 (M+Na) + 318.1101, found 318.1094. (E)-2-Acetamido-4-methylstyryl 4-nitrobenzoate (3af): yellow solid; mp 223-224 o C; yield 84% (57.0 mg); 1 H NMR (500 MHz, DMSO) δ 9.52 (s, 1H), 8.40 (d, J = 8.2 Hz, 2H), 8.31 (d, J = 8.3 Hz, 2H), 7.95 (d, J = 12.5 Hz, 1H), 7.51 (d, J = 7.6 Hz, 1H), 7.25 (s, 1H), 7.00 (d, J = 7.2 Hz, 1H), 6.82 (d, J = 12.5 Hz, 1H), 2.28 (s, 3H), 2.08 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 168.6, 161.7, 150.6, 137.5, 136.4, 135.4, 133.7, 131.1, 126.8, 126.4, 125.7, 124.8, 124.1, 113.1, 23.3, 20.7; HRMS m/z (ESI) calcd. for C 18H 16N 2NaO + 5 (M+Na) + 363.0951, found 363.0945. N-Acetyl-6-methyl-indole (5a): 1 colorless liquid; yield 89% (30.9 mg, starting from 3aa), 61% (21.3 mg, one-pot process); 1 H NMR (500 MHz, CDCl 3) δ 8.30 (s, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.33 (d, J = 3.6 Hz, 1H), 7.11 (dd, J = 7.9, 0.8 Hz, 1H), 6.59 (dd, J = 3.8, 0.5 Hz, 1H), 2.61 (s, 3H), 2.50 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 168.8, 136.1, 135.3, 128.2, 125.2, 124.7, 120.5, 116.9, 109.2, 24.0, 22.0. S10

1-(6-Bromo-1H-indol-1-yl)ethan-1-one (5j): 2 colorless crystal; yield 57% (27.3 mg); 1 H NMR (500 MHz, CDCl 3) δ 8.64 (s, 1H), 7.39 (s, 1H), 7.38 (d, J = 1.6 Hz, 1H), 7.37 (d, J = 3.4 Hz, 1H), 6.59 (dd, J = 3.7, 0.5 Hz, 1H), 2.61 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 168.6, 136.2, 129.3, 127.0, 125.8, 122.0, 120.0, 118.9, 109.0, 23.9. 1-(6-nitro-1H-indol-1-yl)ethan-1-one (5m): 3 yellow solid; yield 63% (25.8 mg); 1 H NMR (500 MHz, DMSO) δ 9.12 (d, J = 2.2 Hz, 1H), 8.22 (d, J = 3.7 Hz, 1H), 8.12 (dd, J = 8.7, 2.2 Hz, 1H), 7.82 (d, J = 8.7 Hz, 1H), 6.92 (dd, J = 3.7, 0.7 Hz, 1H), 2.70 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 169.9, 144.3, 135.4, 133.5, 132.9, 121.3, 118.4, 111.6, 107.9, 23.6. 1-(7-Methyl-1H-indol-1-yl)ethan-1-one (5n): 4 colorless solid; yield 48% (16.5 mg); 1 H NMR (500 MHz, CDCl 3) δ 7.41 (d, J = 7.6 Hz, 1H), 7.38 (d, J = 3.8 Hz, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.16 (d, J = 7.3 Hz, 1H), 6.63 (d, J = 3.8 Hz, 1H), 2.66 (s, 3H), 2.59 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 167.8, 135.3, 132.2, 128.4, 126.9, 126.6, 124.2, 118.6, 109.2, 24.6, 22.8. N-Acetylindole (5p): 1 colorless liquid; yield 93% (29.5 mg, starting from 3pa); 1 H NMR (500 MHz, DMSO) δ 8.34 (d, J = 8.2 Hz, 1H), 7.83 (d, J = 3.8 Hz, 1H), 7.61 (d, J = 7.7 Hz, 1H), 7.31 (td, J = 7.5, 0.9 Hz, 1H), 7.25 (td, J = 7.6, 1.0 Hz, 1H), 6.73 (d, J = 3.7 Hz, 1H), 2.64 (s, 3H); 13 C NMR (126 MHz, DMSO) δ 169.5, 134.9, 130.3, 127.1, 124.5, 123.3, 120.8, 115.8, 108.1, 23.7. 1-(1H-benzo[g]indol-1-yl)ethan-1-one (5t): pale gray solid; mp 89-90 o C; yield 60% (25.1 mg); 1 H NMR (500 MHz, CDCl 3) δ 8.71 (d, J = 8.7 Hz, 1H), 7.92 (d, J = 7.9 Hz, 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.63 (d, J = 8.4 Hz, 1H), 7.55 (ddd, J = 8.5, 6.9, 1.4 Hz, 1H), 7.50 7.46 (m, 2H), 6.73 (d, J = 3.7 Hz, 1H), 2.76 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 169.3, 132.8, 131.3, 129.5, 128.9, 126.5, 126.3, 125.4, 124.8, 124.1, 119.9, 109.6, 25.2; HRMS m/z (ESI) calcd. for C 14H 11NNaO + (M+Na) + 232.0733, found 232.0731. 1-(3H-benzo[e]indol-3-yl)ethan-1-one (5u): colorless solid; mp 105-106 o C; yield 72% (30.1 mg); 1 H NMR (500 MHz, CDCl 3) δ 8.96 (s, 1H), 8.04 7.98 (m, 2H), 7.94 7.91 (m, 1H), 7.50 (s, 1H), 7.49 7.43 (m, 2H), 6.74 (dd, J = 3.9, 0.5 Hz, 1H), 2.64 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 168.2, 135.0, 132.1, 130.9, S11

130.8, 128.9, 128.3, 128.0, 125.1, 124.9, 118.8, 114.1, 109.4, 24.0; HRMS m/z (ESI) calcd. for C 14H 11NNaO + (M+Na) + 232.0733, found 232.0731. Methyl 1-acetyl-1H-indole-6-carboxylate (5w): 1 colorless solid; yield 84% (36.5 mg); 1 H NMR (500 MHz, CDCl 3) δ 9.07 (s, 1H), 7.95 (dd, J = 8.2, 1.5 Hz, 1H), 7.56 (dd, J = 8.2, 0.5 Hz, 1H), 7.54 (d, J = 3.7 Hz, 1H), 6.64 (dd, J = 3.7, 0.7 Hz, 1H), 3.93 (s, 3H), 2.64 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 168.5, 167.6, 135.1, 134.2, 128.2, 127.0, 125.0, 120.6, 118.3, 108.9, 52.1, 24.0. 6-methyl-1H-indole (6a): pale yellow solid; yield 82% (21.5 mg); 1 H NMR (500 MHz, CDCl 3) δ 7.94 (s, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.19 (s, 1H), 7.14 7.09 (m, 1H), 7.01 (d, J = 8.0 Hz, 1H), 6.59 6.45 (m, 1H), 2.51 (s, 3H); 13 C NMR (126 MHz, CDCl 3) δ 136.4, 131.9, 125.8, 123.6, 121.8, 120.5, 111.1, 102.5, 21.8. Indole (6p): colorless crystal; yield 96% (22.5 mg); 1 H NMR (400 MHz, acetone) δ 10.20 (s, 1H), 7.60 (dd, J = 7.9, 1.0 Hz, 1H), 7.45 (ddd, J = 8.2, 1.8, 0.9 Hz, 1H), 7.33 7.30 (m, 1H), 7.13 (ddd, J = 8.2, 7.1, 1.2 Hz, 1H), 7.04 (ddd, J = 8.0, 7.1, 1.1 Hz, 1H), 6.50 (ddd, J = 3.0, 2.0, 0.9 Hz, 1H); 13 C NMR (101 MHz, acetone) δ 137.2, 129.1, 125.5, 122.0, 121.0, 119.9, 112.1, 102.3. 4) References (1). Stuart, D. R.; Fagnou, K. Science 2007, 316, 1172. (2). (a) Kawasaki, T.; Nonaka, Y.; Matsumura, K.; Monai, M.; Sakamoto, M. Synth. Commun. 1999, 29, 3251-3261; (b) Parkan, K.; Pohl, R.; Kotora, M. Chem. Eur. J. 2014, 20, 4414-4419. (3). Wei, Y.; Li, Y.; Zhang, G.; Qiu, G.; Hu, S.; Chen, L.; Li, S.; Zhang, Q. PCT Int. Appl. (2016), WO 2016029839 A1 20160303. (4). Benkovics, T.; Guzei, I. A.; Yoon, T. P., Angew. Chem., Int. Ed. 2010, 49, 9153-9157. S12

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