Supporting Information

Transcript

1 Supporting Information Palladium Catalyzed Decarboxylative Arylation of C-H Bonds by Aryl Acylperoxides Wing-Yiu Yu*, Wing ga Sit, Zhongyuan Zhou and Albert S. C. Chan pen Laboratory of Chirotechnology of the Institute of Molecular Technology for Drug Discovery and Synthesis and the Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong Table of Content 1 General experimental section S1 2 Experimental procedures and characterizations S References S15 4 Screening studies for the Pd-catalyzed arylation S H and 13 C MR spectra S X-ray crystallographic analysis for 2-(4'-nitro[1,1'-biphenyl]-2-yl)-pyridine (6k) S55-57

2 1. General Experimental Section: 2-Arylpyridines were prepared by reacting the analogous arylboronic acids with 2-bromopyridines using reported procedures. 1 Aryl acylperoxides were prepared by reacting acid chlorides with hydrogen peroxide (35 wt. % in H 2 ) and sodium hydroxide by the reported procedures. 2 2-enylpyridine (1a), 2-(p-Tolyl)pyridine (1c), 4-(2-Pyridyl)benzaldehyde (1d), 8-Methlquinoline (1i), Benzo[h]quinoline (1j), 4,4-Dimethyl-2-phenyl-2-oxazoline (1k) were obtained commercially and used as received. Benzoyl peroxide (Luperox A75) was obtained commercially and used as received. Thin layer chromatography was performed on silica gel plates. Silica gel (Merck, mesh) and aluminum oxide (Merck, mesh) were used for flash column chromatography. 1 H and 13 C MR spectra were recorded on a Brüker (400 MHz) spectrometer, chemical shift (δ) values are given in ppm and are referenced to the residual solvent peaks. Coupling constants (J) were reported in hertz (Hz). Mass spectra and high resolution mass spectra (HRMS) were obtained on a VG MICRMASS Fison VG platform, a Finnigan Model Mat 95 ST instrument, or a Brüker APEX 47e FT-ICR mass spectrometer. Melting points were measured on a BUCHI Melting Point B-545 machine. X-ray crystal structure of 2-(4'-nitro[1,1'-biphenyl]-2-yl)-pyridine (6k) was obtained by a Brüker CCD area detector diffractometer. 2. General Experimental Procedures and Characterizations: 2.1 General procedures for the Pd(Ac) 2 -catalyzed Arylations: Method A: A mixture of substrate (0.5 mmol), Pd(Ac) 2 (0.025 mmol, 5 mol%), benzoyl peroxide [1 mmol; addition interval: equiv / 0.5 h] in acetonitrile (1 ml) and acetic acid (1 ml) was sealed in a 8 ml vial with a Teflon lined cap. The mixture was heated at 100 o C (oil bath temperature) for 2 h. After cooling down to room temperature, the reaction mixture was filtered through a plug of silica gel, and the filtrate was concentrated under vacuum to afford an oily substance. The crude product was dissolved in ethyl acetate and treated by saturated aqueous ahc 3 (3 10 ml) solution and extracted with dichloromethane (4 10 ml). The combined organic extracts were dried over a 2 S 4 and evaporated to dryness by a rotary evaporator. The residue was loaded onto a silica gel column for flash column chromatography. Method B: A mixture of substrate (0.5 mmol), Pd(Ac) 2 (0.025 mmol, 5 mol%), benzoyl peroxide [1 mmol] in acetonitrile (1 ml) and acetic acid (1 ml) was sealed in -S1-

3 a 8 ml vial with a Teflon lined cap. The mixture was heated at 160 o C (oil bath temperature) for 10 min. After cooling down to room temperature, the reaction mixture was filtered through a plug of silica gel, and the filtrate was concentrated under vacuum to afford an oily substance. The crude product was dissolved in ethyl acetate and treated by saturated aqueous ahc 3 (3 10 ml) solution and extracted with dichloromethane (4 10 ml). The combined organic extracts were dried over a 2 S 4 and evaporated to dryness by a rotary evaporator. The residue was loaded onto a silica gel column for flash column chromatography. Method C: A mixture of substrate (0.5 mmol), Pd(Ac) 2 (0.05 mmol, 10 mol%), benzoyl peroxide [1 mmol] in acetonitrile (2 ml) was sealed in a 8 ml vial with a Teflon lined cap. The mixture was heated at 160 o C (oil bath temperature) for 10 min. After cooling down to room temperature, the reaction mixture was filtered through a plug of silica gel, and the filtrate was concentrated under vacuum to afford an oily substance. The crude product was dissolved in ethyl acetate and treated by saturated aqueous ahc 3 (3 10 ml) solution and extracted with dichloromethane (4 10 ml). The combined organic extracts were dried over a 2 S 4 and evaporated to dryness by a rotary evaporator. The residue was loaded onto a silica gel column for flash column chromatography. Caution: All the aryl acylperoxides are potentially explosive and that they should be handled with care and in small quantities. (2a) 3 Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 81%. The product was obtained as a yellow oil (76% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.63 (d, J = 4.5 Hz, 1H), (m, 1H), (m, 3H), 7.38 (dt, J = 7.6, 1.7 Hz, 1H), (m, 3H), (m, 2H), (m, 1H), 6.88 (d, J = 7.9 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.9(C), 150.1(C-H), 142.0(C), 141.3(C), 140.1(C), 135.9(C-H), 131.1(C-H), 130.4(C-H), 129.2(C-H), 128.7(C-H), 128.3(C-H), 127.4(C-H), 126.1(C-H), 122.0(C-H). MS (EI): 230(M +, 100), 2028 (10), 115 (5). HRMS (ESI): calcd. for C 17 H 13 H + : , found: S2-

4 (2b) 3b, 3c, 4 Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 91%. The product was obtained as a yellow oil (82% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.50 (d, J = 4.4 Hz, 1H), (m, 4H), 7.28 (d, J = 7.6 Hz, 1H), (m, 5H), 7.08 (dd, J = 7.5, 4.9 Hz, 1H), 1.76 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 160.0(C), 147.1(C-H), 141.6(C), 141.2(C), 140.0(C), 138.0(C-H), 132.2(C-H), 130.4(C-H), 130.2(C-H), 129.8(C-H), 129.2(C-H), 129.0(C-H), 128.8(C-H), 128.3(C-H), 113.9(C-H), 19.4(CH 3 ). MS (EI): 244(M +, 100), 230 (85), 202 (10). HRMS (ESI): calcd. for C 18 H 15 H + : , found: [note: double arylation product (10 % based on conversion) was detected by GCMS] (2c) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 80%. The product was obtained as a yellow oil (73% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.62 (d, J = 4.8 Hz, 1H), 7.61 (d, J = 7.8 Hz, 1H), 7.35 (dt, J = 7.7, 1.7 Hz, 1H), (m, 5H), (m, 2H), (m, 1H), 6.85 (d, J = 8.0 Hz, 1H), 2.45 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.9(C), 150.0(C-H), 142.2(C), 141.1(C), 139.0(C), 137.4(C), 135.8(C-H), (C-H), (C-H), 131.1(C-H), 130.4(C-H), 129.1(C-H), 128.7(C-H), 127.3(C-H), 126.1(C-H), 121.8(C-H), 21.9(CH 3 ). MS (EI): 244(M +, 100), 228 (5), 202 (3). HRMS (ESI): calcd. for C 18 H 15 H + : , found: CH (2d) 4b Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 65%. The product was obtained as a yellow solid (80% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 10.1 (s, 1H), 8.67 (d, J = 4.8 Hz, 1H), (m, 2H), 7.88 (d, J = 7.8 Hz, 1H), 7.43 (dt, J = 7.7, 1.7 Hz, 1H), (m, 3H), (m, 3H), 6.92 (d, J = 7.9 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 192.7(C=), 158.6(C),.150.4(C-H), 145.7(C), 142.2(C), 140.7(C), 136.8(C), 136.1(C-H), 132.7(C-H), 130.2(C-H), 129.2(C-H), 129.0(C-H), 128.0(C-H), 126.0(C-H), 122.8(C-H). MS (EI): 258(M +, 100), 228 (10), 152 (5). HRMS (ESI): calcd. for C 18 H 13 H + : , found: S3-

5 3b, 4b (2e) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 87%. The product was obtained as a yellow oil (73% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.65 (d, J = 4.8 Hz, 1H), 7.54 (s, 1H), (m, 2H), 7.29 (d, J = 6.2 Hz, 1H), (m, 3H), (m, 2H), (m, 1H), 6.86 (d, J = 7.9 Hz, 1H) (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 160.0(C), 150.0(C-H), 141.9(C), 139.9(C), 138.4(C), 138.0(C), 135.8(C-H), 132.2(C-H), 131.7(C-H), 131.2(C-H), 130.4(C-H), 129.9(C-H), 128.7(C-H), 128.2(C-H), 127.1(C-H), 126.1(C-H), 121.9(C-H), 21.7(CH 3 ). MS (EI): 244(M +, 100), 228 (5), 152 (5). HRMS (ESI): calcd. for C 18 H 15 H + : , found: (2f) 5 Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate Me conversion: 68%. The product was obtained as a yellow oil (71 % yield based on conversion.). 1 H MR (400 MHz, CDCl 3 ): δ H 8.64 (d, J = 4.2 Hz, 1H), (m, 1H), 7.26 (s, 1H), 7.25 (d, J = 2.7 Hz, 1H), (m, 2H), (m, 4H), 7.02 (dd, J = 8.5, 2.7 Hz, 1H), 6.87 (d, J = 7.9 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.8(C), 150.1(C), 141.8(C-H), 141.2(C), 135.9(C), 133.9(C-H), 132.4(C-H), 130.5(C-H), 128.7(C-H), 128.3(C-H), 127.9(C-H), 127.3(C-H), 127.0(C-H), 126.1(C-H), 122.1(C-H), 115.7(C-H), 115.6(C-H), 56.2(CH 3 ). MS (EI): 260(M +, 100), 217 (40), 108 (5). HRMS (ESI): calcd. for C 18 H 15 H + : , found: [note: double arylation product (12 % based on conversion) was detected by GCMS] (2g) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate CF 3 conversion: 88%. The product was obtained as a yellow oil (69 % yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.66 (d, J = 4.6 Hz, 1H), 8.00(s, 1H), 7.71 (d, J = 7.9 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), (m, 1H), 7.26 (d, J = 3.8 Hz, 3H), (m, 3H), 6.88 (d, J = 7.8 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 158.4(C), 150.3(C-H), 144.7(C), 140.6(C), 136.1(C-H), 131.8(C-H), 130.3(C-H), 129.7(C-H), 129.0(C-H), 128.4(C-H), 128.1(C-H), 125.9(C-H), 125.8(CF 3 ), 122.6(C-H). MS (EI): 298(M +, 100), 228 (5), 202 (5). HRMS (ESI): calcd. for C 18 H 12 2 F 3 H + : , found: [note: double arylation product (13 % based on conversion) was detected by GCMS] -S4-

6 (2h) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate F conversion: 87%. The product was obtained as a yellow oil (77% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.64 (d, J = 4.7 Hz, 1H), 7.45 (dd, J = 9.6, 2.7 Hz, 1H), (m, 2H), (m, 3H), (m, 4H), 6.86 (d, J = 7.9 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 164.1(CF), 161.7(C), 158.6(C),150.2(C-H), 141.0(C), 137.3(C), 136.0(C-H), 132.8(C-H), 130.7(C-H), 130.3(C-H), 129.7(C-H), 128.8(C-H), 122.5(C-H), 118.0(C-H), 117.7(C-H), 116.1(C-H), 116.0(C-H). MS (EI): 248(M +, 100), 220 (5), 161 (5). HRMS (ESI): calcd. for C 17 H 12 FH + : , found: b, 5, 6 (2i) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 65%. The product was obtained as an orange solid (81% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.97 (dd, J = 4.2, 1.7 Hz, 1H), 8.18 (dd, J = 8.3, 1.8 Hz, 1H), 8.14 (dd, J = 8.2, 1.3 Hz, 2H), 7.85 (dd, J = 7.0, 0.8 Hz, 1H), 7.81 (d, J = 8.2 Hz, 1H), (m, 2H), (m, 3H), 6.14 (s, 2H). 13 C MR (100 MHz, CDCl 3 ): δ C 167.2(C), 150.5(C-H), 146.8(C), 136.8(C), 135.2(C-H), 133.6(C-H), 131.1(C), 130.4(C-H), 129.0(C-H), 128.8(C-H), 128.6(C-H), 126.9(C-H), 122.0(C-H), 63.9(CH 2 ). MS (EI): 218(M +, 100), 204 (5), 189 (5), 108 (15). HRMS (ESI): calcd. for C 16 H 12 H + : , found: (2j) 3b, 5 Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 52%. The product was obtained as a yellow oil (78% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.44 (dd, J = 4.1, 1.7 Hz, 1H), 8.09 (dd, J = 8.0, 1.7 Hz, 1H), 7.94 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 8.8 Hz, 1H), (m, 2H), 7.57 (d, J = 7.2 Hz, 1H), (m, 5H), 7.33 (q, J = 4.1 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 147.5(C), 147.1(C), 142.4(C), 135.9(C-H), 132.1(C), 129.7(C-H), 129.4(C-H), 128.9(C-H), 128.6(C-H), 128.0(C-H), 127.9(C-H), 127.7(C-H), 127.0(C-H), 126.6(C-H), 126.4(C-H), 121.7(C-H). MS (EI): 254(M +, 100), 226 (5), 127 (10). HRMS (ESI): calcd. for C 19 H 13 H + : , found: S5-

7 (2k) 7 Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 72%. The product was obtained as a yellow oil (79% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 7.72 (d, J = 7.9 Hz, 1H), 7.49 (t, J = 7.5 Hz, 2H), (m, 6H), 3.80 (s, 2H), 1.29 (s, 6H). 13 C MR (100 MHz, CDCl 3 ): δ C 164.5(C=), 142.3(C), 141.8(C), 132.1(C), 131.8(C-H), 130.3(C-H), 130.1(C-H), 129.0(C-H), 128.7(C-H), 128.2(C-H), 127.5(C-H), 80.2(CH 2 ), 68.2(C), 29.0(CH 3 ). MS (EI): 250(M +, 100), 207 (10), 196 (10). HRMS (ESI): calcd. for C 17 H 17 H + : , found: Me (4a) Eluant: 90% n-hexane/ 10% ethyl acetate. Substrate conversion: 71%. The product was obtained as a yellow oil (80% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 7.73 (d, J = 8.4 Hz, 1H), 7.60 (dd, J = 7.7, 2.3 Hz, 4H), 7.45 (t, J = 7.4 Hz, 3H), 7.37 (d, J = 8.3 Hz, 1H), 4.02 (s, 3H), 1.68 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 158.9(C=), 141.8(C), 141.1(C), 137.5(C), 134.2(C-H), 130.9(C-H), 130.3(C-H), 129.6(C-H), 129.2(C-H), 127.9(C-H), 122.4(C-H), 62.4(CH 3 ), 17.1(CH 3 ). MS (EI): 224(M +, 100), 194 (95), 178 (40), 152 (60). HRMS (ESI): calcd. for C 15 H 15 H + : , found: (4b) Eluant: 90% n-hexane/ 10% ethyl acetate. Substrate Me conversion: 62%. The product was obtained as a yellow oil (81% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 7.44 (d, J = 4.1 Hz, 1H), (m, 1H), (m, 3H), 4.04 (s, 3H), 2.46 (s, 3H), 1.67 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.2(C=), 141.7(C), 138.3(C), 137.8(C), 137.2(C), 130.9(C-H), 130.5(C-H), 130.1(C-H), 129.6(C-H), 128.8(C-H), 127.1(C-H), 62.4(CH 3 ), 21.6(CH 3 ), 17.2(CH 3 ). MS (EI): 238(M +, 90), 223 (10), 208 (100), 193 (15). HRMS (ESI): calcd. for C 16 H 17 H + : , found: S6-

8 Me (5) Eluant: 90% n-hexane/ 10% ethyl acetate. Substrate conversion: 63%. The product was obtained as a yellow oil (85% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 7.69 (d, J = 8.3 Hz, 1H), 7.49 (d, J = 8.3 Hz, 1H), (m, 3H), C (m, 1H), 3.91 (s, 3H), 1.69 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 157.5(C=), 146.7(C), 139.2(C), 137.5(C), 132.8(C-H), 130.7(C-H), 130.4(C-H), 129.8(C-H), 129.2(C-H), 127.4(C-H), 119.5(C ), 111.7(C), 62.5(CH 3 ), 17.3(CH 3 ). MS (EI): 249(M +, 100), 234 (20), 219 (80), 204 (30). HRMS (ESI): calcd. for C 16 H 14 2 H + : , found: (6a) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 70%. The product was obtained as a yellow oil (84% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.58 (d, J = 4.5 Hz, 1H), 7.89 (d, J = 7.6 Hz, 1H), (m, 3H), (m, 3H), Cl (m, 2H), (m, 1H), 6.93 (d, J = 7.8 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.1(C), 149.9(C-H), 140.8(C), 140.6(C), 138.4(C), 135.9(C-H), 133.8(C-Cl), 132.6(C-H), 131.4(C-H), 130.6(C-H), 130.0(C-H), 129.0(C-H), 128.9(C-H), 128.7(C-H), 126.4(C-H), 124.8(C-H), 122.0(C-H). MS (EI): 264(M +, 1), 230 (100), 202 (10). HRMS (ESI): calcd. for C 17 H 12 ClH + : , found: (6b) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 87%. The product was obtained as a yellow oil (83% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.62 Cl (d, J = 4.6 Hz, 1H), 7.69 (d, J = 7.1 Hz, 1H), (m, 4H), 7.20 (t, J = 7.7 Hz, 2H), 7.11 (t, J = 7.2 Hz, 2H), 6.95 (q, J = 7.1 Hz, 2H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.5(C), 150.1(C-H), 143.8(C), 140.1(C), 139.8(C), 136.0(C-H), 134.5(C-Cl),131.2(C-H), 130.9(C-H), 130.2(C-H), 129.8(C-H), 129.2(C-H), 128.7(C-H), 128.6(C-H), 127.4(C-H), 125.8(C-H), 122.2(C-H). MS (EI): 264(M +, 100), 228 (10), 202 (1). HRMS (ESI): calcd. for C 17 H 12 ClH + : , found: S7-

9 (6c) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 85%. The product was obtained as a white solid (83% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.62 (d, J = 4.7 Hz, 1H), (m, Cl 1H), (m, 4H), 7.20 (d, J = 8.4 Hz, 2H), (m, 3H), 6.91 (d, J = 8.0 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.6(C), 150.1(C-H), 140.4(C), 140.1(C), 140.0(C), 136.1(C-H), 133.4(C-H), 131.5(C-H), 131.2(C-H), 131.1(C-H), 129.2(C-H), 128.9(C-H), 128.7(C-H), 125.8(C-H), 122.1(C-H). MS (EI): 264(M +, 100), 228 (10), 202 (5). HRMS (ESI): calcd. for C 17 H 12 ClH + : , found: (6d) 3b Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 78%. The product was obtained as a white solid (84% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.62 (d, J = 4.8 Hz, 1H), 7.68 (t, J = 4.5 Hz, F 1H), (m, 4H), (m, 3H), (m, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 161.3(C), 150.1(C-H), 140.1(C), 137.9(C), 136.0(C-H), 131.8(C), 131.7(C-H), 131.1(C-H), 131.0(C-H), 129.2(C-H), 128.4(C-H), 125.9(C-H), 122.0(C-H), 115.7(C-H), 115.5(C-H). MS (EI): 248(M +, 100), 228 (5), 220 (10). HRMS (ESI): calcd. for C 17 H 12 FH + : , found: (6e) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 84%. The product was obtained as a yellow oil (75% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.60 (d, J = 4.7 Hz, 1H), (m, 1H), (m, 6H), 7.08 Br (dt, J = 5.0, 0.8 Hz, 1H), 7.01 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 7.9 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.4(C), 150.0(C-H), 140.8(C), 139.9(C), 139.8(C-H), 136.0(C), 132.0(C-H), 131.7(C-H), 131.1(C-H), 129.1(C-H), 128.5(C-H), 127.9(C-H), 125.7(C-H), 122.3(C-H), 122.0(C-Br). MS (EI): 310(M +, 100), 228 (40), 202 (5), 115 (10). HRMS (ESI): calcd. for C 17 H 12 BrH + : , found: S8-

10 (6f) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 65%. The product was obtained as a white solid (82% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.65 (d, J = 4.2 Hz, 1H), 7.71 (dd, J = 5.5, 2.7 Hz, 1H), (m, 3H), 7.38 (dt, J = 7.7, 1.5 Hz, 1H), (m, 5H), 6.92 (d, J = 7.9 Hz, 1H), 2.33 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 160.0(C), 150.0(C-H), 141.1(C), 140.0(C), 139.0(C), 137.0(C-H), 135.8(C-H), 131.1(C-H), 130.2(C-H), 129.4(C-H), 128.0(C-H), 126.0(C-H), 121.9(C-H), 21.7(CH 3 ). MS (EI): 244(M +, 100), 228 (5), 202 (3). HRMS (ESI): calcd. for C 18 H 15 H + : , found: (6g) 3b Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 76%. The product was obtained as a white solid (81% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.65 (d, J = 4.2 Hz, 1H), 7.71 (dd, J = 5.5, 2.7 Hz, 1H), (m, 3H), 7.38 (dt, J = 7.7, 1.5 Hz, 1H), (m, 5H), 6.92 (d, J = 7.9 Hz, 1H), 2.33 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 160.0(C), 150.0(C-H), 141.1(C), 140.0(C), 139.0(C), 137.0(C-H), 135.8(C-H), 131.1(C-H), 130.2(C-H), 129.4(C-H), 128.0(C-H), 126.0(C-H), 121.9(C-H), 21.7(CH 3 ). MS (EI): 244(M +, 100), 228 (5), 202 (3). HRMS (ESI): calcd. for C 18 H 15 H + : , found: (6h) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 88%. The product was obtained as a yellow oil (84% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.61 (d, J = 4.8 Hz, 1H), (m, 1H), (m, 5H), F 3 C (m, 1H), 7.27 (d, J = 7.7 Hz, 2H), (m, 1H), 6.93 (d, J = 7.8 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.4(C), 150.2(C-H), 145.8(C), 140.3(C), 139.8(C), 136.2(C-H), 131.3(C-H), 131.0(C-H), 130.6(C-H), 129.9(C-H), 129.6(C-H), 129.4(C-H), 129.0(C-H), 126.2(C-H), 125.8(C-H), 125.6(C-H), 123.5(C-H), 122.3(CF 3 ). MS (EI): 298(M +, 100), 280 (1), 228 (5) 202 (3). HRMS (ESI): calcd. for C 18 H 12 F 3 H + : , found: S9-

11 (6i) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 70%. The product was obtained as a yellow oil (81% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.65 (d, J = 4.8 Hz, 1H), (m, 1H), 7.45 (d, J = 3.0 Hz, 3H), 7.36 (dt, J = 7.7, 1.6 Hz, 1H), 7.26 (d, J = 8.3 Hz, 2H), 7.10 (d, J = 8.3 Hz, 3H), 6.90 (d, J = 7.9 Hz, 1H), 1.31 (s, 9H). 13 C MR (100 MHz, CDCl 3 ): δ C 160.0(C), 150.3(C), 150.0(C-H), 141.1(C), 140.0(C), 138.9(C), 135.7(C-H), 135.6(C-H), 131.1(C-H), 130.0(C-H), 129.1(C-H), 128.0(C-H), 126.1(C-H), 125.6(C-H), 121.9(C-H), 35.1(C), 32.0(CH 3 ). MS (EI): 286(M +, 100), 272 (25), 256 (5), 230 (8). HRMS (ESI): calcd. for C 21 H 21 H + : , found: (6j) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 63%. The product was obtained as a white solid (80% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.57 (d, J = 4.4 Hz, 1H), C (m, 1H), (m, 5H), (m, 1H), 7.24 (d, J = 8.3 Hz, 2H), 7.14 (dd, J = 6.8, 5.2 Hz, 1H), 6.95 (d, J = 7.9 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.2(C), 150.2(C-H), 147.0(C), 140.2(C), 139.4(C), 136.4(C-H), 132.5(C-H), 131.3(C-H), 130.9(C-H), 130.8(C-H), 129.4(C-H), 129.3(C-H), 125.7(C-H), 122.4(C-H), 119.5(C-H), 111.0(C ). MS (EI): 255(M +, 100), 227 (5), 201 (1). HRMS (ESI): calcd. for C 18 H 12 2 H + : , found: (6k) Eluant: 80% n-hexane/ 20% ethyl acetate. Substrate conversion: 90%. The product was obtained as a yellow solid (54% yield based on conversion). Melting point: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.57 (d, J = 4.7 Hz, 1H), (d, J = 8.6 Hz, 2H), 7.68 (dd, J = 8.8, 2.1 Hz, 1H), (m, 4H), 7.30 (d, J = 8.7 Hz, 2H), 7.15 (dd J = 7.3, 5.0 Hz, 1H), 6.99 (d, J = 7.8 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C 159.2(C), 150.2(C-H), 149.1(C-), 147.2(C), 140.4(C), 139.0(C), 136.5(C-H), 131.4(C-H), 131.1(C-H), 130.9(C-H), (C-H), (C-H), 125.6(C-H), 123.9(C-H), 122.5(C-H). MS (EI): 275(M +, 100), 229 (65), 217 (5), 202 (10). HRMS (ESI): calcd. for C 17 H H + : , found: S10-

12 (7a) 8 Eluant: 60% n-hexane/ 40% diethyl ether. Substrate conversion: 83%. The product was obtained as a yellow oil (90% yield based on conversion). 1 H MR Me (400 MHz, CDCl 3 ): δ H 8.59 (d, J = 4.5 Hz, 1H), 8.03 (d, J = 8.8 Hz, 2H), 7.78 (dd, J = 7.6, 1.5 Hz, 1H), (m, 2H), 7.45 (dt, J = 7.6, 1.5 Hz, 1H), 7.36 (dt, J = 7.5, 0.8 Hz, 1H), 7.29 (dd, J = 7.9, 0.7 Hz, 1H), (m, 1H), 6.91 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 165.4(C=), 164.3(C), 156.1(C), 150.1(C), 148.9(C-H), 136.6(C-H), 133.9(C-H), 132.8(C-H), 131.4(C-H), 130.2(C), 126.8(C-H), 123.9(C-H), 122.6(C), 122.2(C-H), 119.2(C-H), 114.3(C-H), 56.0(CH 3 ). MS (EI): 305(M +, 20), 135 (100). HRMS (ESI): calcd. for C 19 H 15 3 H + : , found: IR (KBr, cm -1 ): 1732cm -1. (7b) 8 Eluant: 60% n-hexane/ 40% diethyl ether. Me Substrate conversion: 67%. The product was obtained as a yellow oil (82% yield based on conversion). 1 H MR (400 MHz, CDCl 3 ): δ H 8.60 (d, J = 4.1 Hz, 1H), 7.78 (dd J = 7.7, 1.5 Hz, 1H), 7.69 (d, J = 6.6 Hz, 1H), (m, 3H), 7.47 (dt J = 7.7, 1.6 Hz, 1H), (m, 2H), 7.32 (dt J = 8.0, 1.0 Hz, 1H), (m, 2H), 3.81 (s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C 165.6(C=), 160.2(C), 156.1(C), 150.2(C), 148.9(C-H), 136.8(C-H), 133.9(C-H), 131.5(C), 131.3(C-H), 130.3(C-H), 130.1(C), 127.0(C-H), 124.3(C-H), 123.9(C-H), 123.2(C-H), 122.8(C-H), 120.7(C-H), 115.0(C-H), 56.0(CH 3 ). MS (EI): 305(M +, 20), 135 (100). HRMS (ESI): calcd. for C 19 H 15 3 H + : , found: IR (KBr, cm -1 ): 1736cm -1. -S11-

13 2.2 Preparation of aryl acylperoxides 2 Hydrogen peroxide (1.669 g, 35 wt. % in H 2, mmol) was added dropwise over 10 min to a cold (ice bath) solution of acid chloride (30mmol) in diethyl ether (7 ml). This was followed by the dropwise addition of an aqueous solution of ah (1.517g, 37.93mmol, 10 ml) over 20 min. The resulting white precipitate was collected by filtration. After washing with water (3 5 ml) and diethyl ether (3 5 ml), the solid was crystallized from a cold acetone / water mixture (1 : 3 v/v). Cl Bis(p-chlorobenzoyl) peroxide. 9 The product was obtained as a white (84% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.99 Cl (d, J = 8.6 Hz, 2H), 7.51 (d, J = 8.6 Hz, 2H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 162.9(C=), 141.8(CCl), 131.8(C-H), 130.1(C-H), 124.6(C). IR (KBr,cm -1 ): 1792, 1758 (C=), 1226 (C-). Bis(m-chlorobenzoyl) peroxide. 10 The product was Cl obtained as a white (80% yield). Melting point: Cl H MR (400 MHz, CD 2 Cl 2 ): δ H 8.02 (s, 1H), 7.94 (d, J = 8.8 Hz, 1H), 7.65 (d, J = 10.0 Hz, 1H), 7.48 (t, J = 7.9 Hz, 1H), 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 162.5(C=), 135.8(CCl), 135.3(C-H), 131.2(C-H), 130.4(C-H), 128.6(C-H), 127.8(C). IR (KBr,cm -1 ): 1790, 1765 (C=), 1219 (C-). Bis(o-chlorobenzoyl) peroxide. The product was obtained Cl as a white (78% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.91 (d, J = 7.9 Hz, 1H), Cl (m, 2H), (m, 1H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 162.6(C=), 134.9(C-H), 134.7(CCl), 132.2(C-H), 132.0(C-H), 127.9(C-H), 126.3(C). IR (KBr,cm -1 ): 1786 (C=), 1225 (C-). F Bis(p-fluorobenzoyl) peroxide. 9 The product was obtained as a white (85% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 8.08 (dd, F J = 8.7, 5.4 Hz, 2H), 7.22 (t, J = 8.7 Hz, 2H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 168.6(CF), 162.9(C=), 133.2(C-H), 122.5(C), 177.0(C-H). IR (KBr,cm -1 ): 1790, 1761 (C=), 1242 (C-). -S12-

14 Br Bis(p-bromobenzoyl) peroxide. The product was obtained as a white (85% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.91 Br (d, J = 8.5 Hz, 2H), 7.68 (d, J = 8.5 Hz, 2H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 163.0(C=), 133.1(C-H), 131.9(C-H), 130.5(C), 125.1(CBr). IR (KBr,cm -1 ): 1791, 1762 (C=), 1227 (C-). Bis(p-methylbenzoyl) peroxide. 9 The product was obtained as a white (86% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.93 (d, J = 8.2 Hz, 2H), 7.33 (d, J = 7.9 Hz, 2H), 2.43 (s, 3H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 163.9(C=), 146.4(C), 130.4(C-H), 123.4(C), 22.3(CH 3 ). IR (KBr,cm -1 ): 1776, 1757 (C=), 1232 (C-). CF Bis(p-trifluoromethylbenzoyl) peroxide. 9 3 The product was obtained as a white (88% yield). Melting point: H MR (400 MHz, F 3 C CD 2 Cl 2 ): δ H 8.19 (d, J = 8.3 Hz, 2H), 7.81 (d, J = 8.4 Hz, 2H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 162.6(C=),136.6(C), 136.2(C), 131.0(C-H), 126.8(C-H), 125.6(CF 3 ). IR (KBr,cm -1 ): 1796, 1768 (C=), 1229 (C-). Bis(p-tert-butylenzoyl) peroxide. 11 The product was obtained as a white (88% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.97 (d, J = 8.6 Hz, 2H), 7.54 (d, J = 8.5 Hz, 2H), 1.34 (s, 9H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 163.8(C=), 159.2(C), 130.2(C-H), 126.7(C-H), 123.4(C), 36.0(C), 31.5(CH 3 ). IR (KBr,cm -1 ): 1784, 1758 (C=), 1233 (C-). C Bis(p-formylbenzoyl) peroxide. 12 The product was obtained as a white (82% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): C δ H 8.16 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8.6 Hz, 2H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 162.2(C=), 133.6(C-H), 133.1(C), 131.0(C-H), 118.8(C), 118.2(C). IR (KBr,cm -1 ): 2235 (C ), 1780 (C=), 1231 (C-). -S13-

15 Bis(p-nitrobenzoyl) peroxide. The product was 2 obtained as a white (84% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H (d, J = 8.8 Hz, 2H), 8.25 (d, J = 8.7 Hz, 2H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 162.0(C=), 152.1(C), 131.8(C-H), 131.4(C), 124.8(C-H). IR (KBr,cm -1 ): 1780 (C=), 1527 (-), 1232 (C-). Bis(o-methylbenzoyl) peroxide. The product was obtained as a white (78% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.92 (d, J = 7.7 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), (m, 2H), 2.62 (s, 3H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 164.9(C=), 141.2(C), 133.9(C), 132.6(C-H), 130.9(C-H), 126.8(C-H), 126.1(C-H), 21.5(CH 3 ). IR (KBr,cm -1 ): 1784, 1762 (C=), 1217 (C-). Me Bis(o-methoxylbenzoyl) peroxide. The product was obtained as a white (81% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 8.08 (dd, J = 7.8, 1.8 Hz, Me 1H), (m, 1H), (m, 2H), 4.04 (s, 3H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 166.0(C=), 158.9(C), 135.8(C-H), 134.0(C-H), 122.7(C-H), 118.3(C-H), 112.6(C), 57.4(CH 3 ). IR (KBr,cm -1 ): 1690, 1669 (C=), 1254 (C-). Bis(m-methoxylbenzoyl) peroxide. The Me product was obtained as a white (84% yield). Me Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 7.64 (d, J = 7.6 Hz, 1H), 7.54 (s, 1H), 7.43 (t, 8.0 Hz, 1H), 7.21 (d, J = 8.3 Hz, 1H), 3.85 (s, 3H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 163.7(C=), 160.7(C), 130.8(C), 127.4(C-H), 122.6(C-H), 121.5(C-H), 114.9(C-H), 56.3(CH 3 ). IR (KBr,cm -1 ): 1787, 1759 (C=), 1266 (C-). Me Me Bis(p-methoxylbenzoyl) peroxide. The product was obtained as a white (84% yield). Melting point: H MR (400 MHz, CD 2 Cl 2 ): δ H 8.00 (d, J = 8.8 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H). 13 C MR (100 MHz, CD 2 Cl 2 ): δ C 165.3(C=), 163.6(C), 132.5(C-H), 118.3(C), 115.0(C-H), 56.4(CH 3 ). IR (KBr,cm -1 ): 1770, 1749 (C=), 1229 (C-). 2 -S14-

16 3. Reference: 1. avarro, H. Kaur, P. Mahjoor, and S. P. olan., J. rg. Chem. 2004, 69, Flowers, G. C.; Leffler, J. E. J. rg. Chem. 1985, 50, (a) Thomas, V.; Armido, S. rg Lett. 2008, 10, 129. (b) Shuichi,.; Susumu, F.; aoki, H.; oboru, W.; Sotaro, M.; Yoshio, I. rg Lett. 2001, 3, (c) Shuichi,.; Susumu, F.; Yoshio, I. Chem Commun. 1998, 22, (a) Kalberer, E. W.; Whitfield, S. R.; Sanford, M. S. J. Mol. Catal. A-Chem. 2006, 251, 108. (b) Kalyani, D.; Deprez,. R.; Desai, L. V.; Sanford, M. S. J. Am. Chem. Soc. 2005, 127, Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2007, 129, Hull, K. L.; Anani, W. Q.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, i, S.; Aizawa, E.; gino, Y.; Inoue, Y. J. rg. Chem. 2005, 70, Dick, A. R.; Kampf, J. W.; Sanford, M. S. J. Am. Chem. Soc. 2005, 127, Buehler, H. xid Commun. 1993, 16, (a) Masahiro, T.; Kosaku, I. Chem. arm. Bull. 2006, 54, (b) Paola, A.; Lucedio, G.; Corrado, R.; Paolo, S.; Giancarlo, M. J. Chem. Soc. Perk T , 9, (c) Hortmann, A. G.; Aron, A. J.; Bhattacharya, A. K. J. rg. Chem. 1978, 43, Moorhoff, C. M.; Braybrook, C. Monatsh. Chem. 2004, 135, Linhardt, R. J.; Murr, B. L.; Montgomery, E.; sby, J.; Sherbine, J. J. rg. Chem. 1982, 47, S15-

17 4. ptimaization Studies for the Pd-Catalyzed Arylation Reaction: Table S1. Screening studies Pd(Ac) 2 (5 mol %) 100 o C entry peroxide solvent time (h) convn (%) Yield (%) 2-phenylpyridine dimer (%) 1 a 2 equiv DCE a 2 equiv DCE equiv CH 3 C equiv / 1 h CH 3 C The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. a Chlorinated products detected by GC/MS. Table S2. Acid effect Pd(Ac) 2 (5 mol %) solvent (2 ml), 100 o C, 4 h 4 x 0.5 equiv / h entry solvent convn (%) yield (%) 1 AcH:CH 3 C (1 :1 v/v) TFA:CH 3 C (1 :1 v/v) AcH AcH:CH 3 C (1 :3 v/v) CH 3 C (2 ml) + AcH (0.1 ml) CH 3 C + 2 equiv Cu(Ac) CH 3 C + 2 equiv FeCl The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. -S16-

18 Table S3. Solvent effect Pd(Ac) 2 (5 mol %) solvent (2 ml), 100 o C, 4 h 4 x 0.5 equiv / h entry solvent convn (%) yield (%) 1 AcH:CH 3 C (1:1 v/v) AcH:DMF (1:1 v/v) AcH:DMS (1:1 v/v) AcH:DCE (1:1 v/v) AcH:THF (1:1 v/v) The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. Table S4. Effect of peroxide addition protocol and reaction time Pd(Ac) 2 (5 mol %) 100 o C, CH 3 C:AcH (1:1 v/v) entry peroxide time (h) convn (%) yield (%) equiv / 1 h equiv equiv equiv equiv / 0.5 h The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. -S17-

19 Table S5. Effect of oxidants Pd(Ac) 2 (5 mol %), 2 h 100 o C, CH 3 C:AcH (1:1 v/v) 4 x 0.5 equiv / 0.5 h entry oxidant convn (%) yield (%) 1 1 equiv TBHP equiv / 1 h TBHP equiv TBHP + 1 equiv Cu(Ac) equiv TBHP + 10mol % Cu(Ac) The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. Table S6. Temperature effect and reaction time Pd(Ac) 2 (5 mol %), 2 h CH 3 C:AcH (1:1 v/v) 4 x 0.5 equiv / 0.5 h entry peroxide temp ( o C) time convn (%) yield (%) equiv / 0.5 h h equiv / 0.5 h 80 2 h equiv / 1 h 80 4 h equiv / 0.5 h h equiv min The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. -S18-

20 Table S7. Catalyst loading Pd(Ac) 2, 2 h CH 3 C:AcH (1:1 v/v) 4 x 0.5 equiv / 0.5 h entry Pd(Ac) 2 temp ( o C) time convn (%) yield (%) 1 1 mol % min mol % min mol % min The reactions were carried out in a 0.5 mmol-scale of 2-phenylpyridine. Conversion and yield were determined by GC/FID using tetradecane as internal standard. The percentage yield is based on conversion. -S19-

21 Table S8. Pd-Catalyzed Arylation of Aromatic C H Bonds R 1 R 2 2 equiv Pd(Ac) 2 (5 mol %) CH 3 C:AcH (1:1 v/v) R 1 R 2 entry R 1 R 2 method convn (%) yield (%) 1 H H A B Me H A B H 4-Me A B H 4-CH A B H 3-Me A B H 3-Me A B H 3-CF 3 A B H 3-F A B Reaction conditions: substrate (0.5 mmol), peroxide (2 equiv), Pd(Ac) 2 (5 mol %). The percentage yield based on conversion. Method A: 100 C for 2 h in CH 3 C (1 ml), AcH (1 ml), peroxide (4 0.5 equiv / 0.5 h). Method B: 160 C for 10 min in CH 3 C (1 ml), AcH (1 ml), peroxide (2 equiv). -S20-

22 Table S9. Arylation of oxazoline with benzoyl peroxide Pd(Ac) 2 (5 mol %) entry peroxide solvent equiv / 0.5 h CH 3 C : AcH = 1 : 1 temp ( o C) time convn (%) yield (%) h # 2 equiv CH 3 C : AcH = 1 : min equiv CH 3 C min # 2 equiv CH 3 C min The reactions were carried out in a 0.5 mmol-scale of oxime. The percentage yield is based on conversion. # 10 mol % Pd(Ac) 2. Table S10. Arylation of -methyl oximes with benzoyl peroxide Me Me Pd(Ac) 2 (5 mol %) entry method convn (%) yield (%) 1 a A b A c C C The reactions were carried out in a 0.5 mmol-scale of oxime. The percentage yield is based on conversion. a It produced a complicated mixture and extensive hydrolysis of the oximes. b CH 3 C as solvent. c 5 mol % Pd(Ac) 2. Method A: 100 C for 2 h in CH 3 C (1 ml), AcH (1 ml), peroxide (4 0.5 equiv / 0.5 h). Method C: 160 C for 10 min in CH 3 C (2 ml), peroxide (2 equiv). -S21-

23 Table S11. Reaction with Various Aryl Acylperoxides R 2 equiv R Pd(Ac) 2 (5 mol %) CH 3 C:AcH (1:1 v/v) R entry R method convn (%) yield (%) 1 2-Cl A B Cl A B Cl A B F A B Br A B Me A B Me A B CF 3 A B t Bu A B C A B A B Me A ~ no nil B ~ no nil 13 * 4-Me A 72 nil 14 3-Me A ~ no nil B ~ no nil 15 2-Me A ~ no nil B ~ no nil 16 2,4,6-trimethyl A ~ no nil B ~ no nil -S22-

24 Reaction conditions: substrate (0.5 mmol), peroxide (2 equiv), Pd(Ac) 2 (5 mol%). The percentage yield based on conversion. * CH 3 C as solvent, formation of Me as product in 90 % yield based on conversion. Method A: 100 C for 2 h in CH 3 C (1 ml), AcH (1 ml), peroxide (4 0.5 equiv / 0.5 h). Method B: 160 C for 10 min in CH 3 C (1 ml), AcH (1 ml), peroxide (2 equiv). -S23-

25 Figures of 1 H and 13 C MR spectra -S24-

26 Figure S1. 1 H MR of 2a Figure S2. 13 C MR of 2a -S25-

27 Figure S3. 1 H MR of 2b Figure S4. 13 C MR of 2b -S26-

28 Figure S5. GC-MS of 2b + double arylation product [244] [320] -S27-

29 Figure S6. 1 H MR of 2c Figure S7. 13 C MR of 2c -S28-

30 Figure S8. 1 H MR of 2d CH Figure S9. 13 C MR of 2d -S29-

31 Figure S10. 1 H MR of 2e Figure S C MR of 2e -S30-

32 Figure S12. 1 H MR of 2f Me Figure S C MR of 2f -S31-

33 Figure S14. GC-MS of 2f + double arylation product Me [260] Me [336] Me -S32-

34 Figure S15. 1 H MR of 2g CF 3 Figure S C MR of 2g -S33-

35 Figure S17. GC-MS of 2g + double arylation product CF 3 [298] CF 3 [374] CF 3 -S34-

36 Figure S18. 1 H MR of 2h F Figure S C MR of 2h -S35-

37 Figure S20. 1 H MR of 2i Figure S C MR of 2i -S36-

38 Figure S22. 1 H MR of 2j Figure S C MR of 2j -S37-

39 Figure S24. 1 H MR of 2k Figure S C MR of 2k -S38-

40 Figure S26. 1 H MR of 4a Me Figure S C MR of 4a -S39-

41 Figure S28. 1 H MR of 4b Me Figure S C MR of 4b -S40-

42 Figure S30. 1 H MR of 5 Me C Figure S C MR of 5 -S41-

43 Figure S32. 1 H MR of 6a Cl Figure S C MR of 6a -S42-

44 Figure S34. 1 H MR of 6b Cl Figure S C MR of 6b -S43-

45 Figure S36. 1 H MR of 6c Cl Figure S C MR of 6c -S44-

46 Figure S38. 1 H MR of 6d F Figure S C MR of 6d -S45-

47 Figure S40. 1 H MR of 6e Br Figure S C MR of 6e -S46-

48 Figure S42. 1 H MR of 6f Figure S C MR of 6f -S47-

49 Figure S44. 1 H MR of 6g Figure S C MR of 6g -S48-

50 Figure S46. 1 H MR of 6h F 3C Figure S C MR of 6h -S49-

51 Figure S48. 1 H MR of 6i Figure S C MR of 6i -S50-

52 Figure S50. 1 H MR of 6j C Figure S C MR of 6j -S51-

53 Figure S52. 1 H MR of 6k 2 Figure S C MR of 6k -S52-

54 Figure S54. 1 H MR of 7a Me Figure S C MR of 7a -S53-

55 Figure S56. 1 H MR of 7b Me Figure S C MR of 7b -S54-

56 X-ray crystallographic analysis for 2-(4'-nitro[1,1'-biphenyl]-2-yl)-pyridine (6k) -S55-

57 Figure S58. The molecular structure of 2-(4'-nitro[1,1'-biphenyl]-2-yl)-pyridine (6k) -S56-

58 Table S12. Crystal data and structure refinement for 6k. Identification code snow18 Empirical formula C 17 H Formula weight Temperature 296(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = (3) Å = 90. b = (2) Å = (10). c = (2) Å = 90. Volume (5) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 576 Crystal size 0.48 x 0.38 x 0.16 mm 3 Theta range for data collection 2.17 to Index ranges -19<=h<=19, -13<=k<=15, -9<=l<=10 Reflections collected Independent reflections 3164 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3164 / 0 / 190 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 -S57-