Supporting Information

Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information 1. General experimental methods (S2). 2. Table 1: Initial studies (S2-S4). 3. General experimental procedure and characterization data (S4-S15). 4. 1 H and 13 C NMR spectra of compounds 3 (S16-S65). S1

General experimental methods: Unless otherwise stated, all commercial reagents were used as received. Flash column chromatography was performed using silica gel (60-Å pore size, 32 63μm, standard grade). Analytical thin layer chromatography was performed using glass plates pre-coated with 0.25 mm 230 400 mesh silica gel impregnated with a fluorescent indicator (254 nm). Thin layer chromatography plates were visualized by exposure to ultraviolet light. Organic solutions were concentrated on rotary evaporators at ~20 Torr at 25 35 C. Nuclear magnetic resonance (NMR) spectra are recorded in parts per million from internal tetramethylsilane on the δ scale. 1 H and 13 C NMR spectra were recorded in CDCl 3 on a Bruker DRX-400 spectrometer operating at 400 MHz and 100 MHz, respectively. All chemical shift values are quoted in ppm and coupling constants quoted in Hz. High resolution mass spectrometry (HRMS) spectra were obtained on a microtof II Instrument. Table 1. Initial studies for the reaction of N-(quinolin-8-yl)benzamide 1a, DABCO (SO 2 ) 2 and 4-methylphenyldiazonium salt 2a a,b entry catalyst solvent temp ( C) additive ligand yield 1 Pd(OAc) 2 DMF 70 - - n.d. 2 Pd(OAc) 2 CH 3 CN 70 - - 20% 3 Pd(OAc) 2 DCE 70 - - 24% 4 Pd(OAc) 2 1,4-dioxane 70 - - n.d. 5 Pd(OAc) 2 (trifluoromethyl)benzene 70 - - 22% 6 Pd(OAc) 2 chlorocyclohexane 70 - - 26% 7 Pd(OAc) 2 (trifluoromethoxy)benzene 70 - - 18% 8 Pd(OAc) 2 bromotrichloromethane 70 - - n.d. 9 Pd(OAc) 2 1-bromo-3-chloropropane 70 - - 34% 10 Pd(OAc) 2 (bromomethyl)benzene 70 - - n.d. 11 Pd(OAc) 2 1,2-dibromoethane 70 - - 17% S2

12 Pd(OAc) 2 CHCl 3 70 - - n.d. 13 Pd(OAc) 2 CCl 4 70 - - n.d. 14 Pd(OAc) 2 DCM 70 - - <10% 15 Pd(OAc) 2 n-c 5 H 11 Br 70 - - <10% 16 Pd(OAc) 2 chlorobenzene 70 - - n.d. 17 Pd(OAc) 2 pentafluorobenzene 70 - - n.d. 18 Pd(OAc) 2 1,3-dichloropropane 70 - - <10% 19 Pd(OAc) 2 dichloro(methoxy)methane 70 - - n.d. 20 Pd(OAc) 2 1,1,2,2-tetrachloroethane 70 - - n.d. 21 PdCl 2 1-bromo-3-chloropropane 70 - - trace 22 Pd(dppf) 2 Cl 2 1-bromo-3-chloropropane 70 - - trace 23 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 - - 40% 24 PdCl 2 (PCy 3 ) 2 1-bromo-3-chloropropane 70 - - trace 25 Pd(norboenene)Cl 2 1-bromo-3-chloropropane 70 - - 39% 26 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 - X-Phos trace 27 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 - XantPhos 31% 28 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 - dppf trace 29 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 - DPEPhos 25% 30 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 50 - - 21% 31 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 80 - - 39% 32 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 100 - - trace 33 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 NaHSO 3-32% 34 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 NaI - 50% 35 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 K 3 PO 4-48% 36 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 NaOAc - 49% 37 Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 DABCO - trace 38 c Pd(CH 2 -CH=CH 2 )Cl 1-bromo-3-chloropropane 70 NaOAc/NaI - 61% 39 c Pd(CH 2 -CH=CH 2 )Cl CH 3 OH 70 NaOAc/NaI - n.d. 40 c Pd(CH 2 -CH=CH 2 )Cl NMP 70 NaOAc/NaI - n.d. 41 c Pd(CH 2 -CH=CH 2 )Cl HFIP 70 NaOAc/NaI - n.d. 42 c Pd(CH 2 -CH=CH 2 )Cl 1,3-dibromopropane 70 NaOAc/NaI - 72% 43 c Pd(CH 2 -CH=CH 2 )Cl benzonitrile 70 NaOAc/NaI - n.d. 44 c Pd(CH 2 -CH=CH 2 )Cl diethyl carbonate 70 NaOAc/NaI - 41% 45 c Pd(CH 2 -CH=CH 2 )Cl dimethyl malonate 70 NaOAc/NaI - 33% 46 c Pd(CH 2 -CH=CH 2 )Cl EtOAc 70 NaOAc/NaI - <10% 47 c Pd(CH 2 -CH=CH 2 )Cl 2-methoxyethyl ether 70 NaOAc/NaI - n.d. 48 c Pd(CH 2 -CH=CH 2 )Cl ethyl isobutyrate 70 NaOAc/NaI - n.d. 49 c Pd(CH 2 -CH=CH 2 )Cl bromochloromethane 70 NaOAc/NaI - trace 50 c Pd(CH 2 -CH=CH 2 )Cl THF 70 NaOAc/NaI - n.d. 51 c Pd(CH 2 -CH=CH 2 )Cl DMAc 70 NaOAc/NaI - n.d. 52 c Pd(CH 2 -CH=CH 2 )Cl ethyl formate 70 NaOAc/NaI - <10% S3

a Reaction conditions: N-(quinolin-8-yl)benzamide 1a (0.2 mmol), aryldiazonium tetrafluoroborate 2a (0.5 mmol), DABSO (1.5 equiv), catalyst (10 mol%), additive (1.0 equiv), solvent (2.0 ml), 70 C, 4 h. b Isolated yield based on N-(quinolin-8-yl)benzamide 1a. c NaOAc 0.5 equiv, NaI 0.5 equiv. General experimental procedure for the palladium-catalyzed direct C-H ortho-sulfonylation via the insertion of sulfur dioxide. R O H N H 1 DABCO (SO 2 ) 2 Ar N 2 BF 4 N 2 H Pd(C 3 H 5 )Cl (10 mol %) NaOAc/NaI, 70 ο C Br(CH 2 ) 3 Br R R + O Q N H 3 SO 2 Ar O N Ar N N H SO 2 Ar N 3' 8-Aminoquinoline amide 1 (0.2 mmol), DABCO. (SO 2 ) 2 (1.5 equiv.), aryldiazonium tetrafluoroborate 2 (2.5 equiv.), Pd(C 3 H 5 )Cl (10 mol %), NaOAc (0.5 equiv.), and NaI (0.5 equiv.) were added to a dry tube under N 2 atmosphere. Then 1-bromo-3-chloropropane (2.0 ml) was added as the solvent. The mixture was stirred at 70 C for 4 hours. After completion of reaction as indicated by TLC, the solvent was evaporated. The residue was purified directly by flash column chromatography (EtOAc/n-hexane, 1:2) to give the desired product 3 or 3. N-(Quinolin-8-yl)-2-tosylbenzamide 3a 1 1 H NMR (400 MHz, DMSO-d 6 ) δ 2.30 (s, 3H), 7.33 (d, J = 7.7 Hz, 2H), 7.65 (dd, J 1 = 7.9 Hz, J 2 = 4.0 Hz, 1H), 7.70 (t, J = 7.9 Hz, 1H), 7.75-7.83 (m, 4H), 7.86 (d, J = 7.8 Hz, 2H), 8.18 (d, J = 7.6 Hz, 1H), 8.46 (d, J = 8.1 Hz, 1H), 8.72 (d, J = 7.4 Hz, 1H), 8.84 (s, 1H), 10.18 (s, 1H); 13 C NMR (100 MHz, DMSO-d 6 ) δ 21.4, 117.5, 122.7, 123.1, 127.4, 128.3, 129.2, 130.1, 131.2, 134.5, 134.6, 136.9, 137.1, 138.4, 138.5, 144.7, 149.5, 165.9. S4

2-Methyl-N-(quinolin-8-yl)-6-tosylbenzamide 3b 1 H NMR (400 MHz, CDCl 3 ) δ 2.28 (s, 3H), 2.44 (s, 3H), 7.15 (d, J = 8.1 Hz, 2H), 7.42 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.48 (d, J = 4.7 Hz, 2H), 7.56-7.64 (m, 2H), 7.83 (d, J = 8.1 Hz, 2H), 8.02 (t, J = 4.5 Hz, 1H), 8.17 (d, J = 7.5 Hz, 1H), 8.69 (d, J = 3.0 Hz, 1H), 8.95 (d, J = 7.1 Hz, 1H), 9.88 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 19.3, 21.5, 116.9, 121.6, 122.2, 127.0, 127.4, 127.9, 128.2, 129.5, 129.6, 134.3, 135.5, 136.2, 136.3, 137.2, 138.3, 138.4, 138.8, 144.1, 148.2, 165.4; HRMS (ESI) calcd for C 24 H 20 N 2 O 3 S: (M + H + ) 417.1267, found: 417.1274. 5-Methyl-N-(quinolin-8-yl)-2-tosylbenzamide 3c 1 H NMR (400 MHz, CDCl 3 ) δ 2.28 (s, 3H), 2.41 (s, 3H), 7.16 (d, J = 8.0 Hz, 2H), 7.37-7.43 (m, 3H), 7.54-7.59 (m, 2H), 7.85 (d, J = 8.0 Hz, 2H), 8.06 (d, J = 8.1 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.70 (d, J = 3.0 Hz, 1H), 8.88 (d, J = 7.0 Hz, 1H), 10.05 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.4, 21.5, 117.0, 121.7, 122.2, 127.3, 127.9, 128.2, 129.3, 129.5, 129.7, 130.8, 134.4, 136.0, 136.3, 137.0, 138.4, 144.0, 144.6, 148.3, 165.8; HRMS (ESI) calcd for C 24 H 20 N 2 O 3 S: (M + H + ) 417.1267, found: 417.1286. 4-Methyl-N-(quinolin-8-yl)-2-tosylbenzamide 3d 1 H NMR (400 MHz, CDCl 3 ) δ 2.29 (s, 3H), 2.47 (s, 3H), 7.18 (d, J = 8.0 Hz, 2H), 7.41-7.45 (m, 2H), 7.51-7.62 (m, 3H), 7.87 (d, J = 8.1 Hz, 2H), 8.02 (s, 1H), 8.16 (d, J = 7.4 Hz, 1H), 8.71 (d, J = 2.9 Hz, 1H), 8.86 (d, J = 6.4 Hz, 1H), 10.03 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.3, 21.5, 116.9, 121.6, 122.1, 127.3, 127.9, 128.3, 128.7, 129.5, 129.9, 133.9, 134.4, 136.2, 138.1, 138.4, 138.8, 140.9, 144.1, 148.2, 165.8; HRMS (ESI) calcd for C 24 H 20 N 2 O 3 S: (M + H + ) 417.1267, found: 417.1284. S5

N-(Quinolin-8-yl)-2-tosyl-4-(trifluoromethyl)benzamide 3e 1 H NMR (400 MHz, CDCl 3 ) δ 2.31 (s, 3H), 7.22 (d, J = 8.1 Hz, 2H), 7.45 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.59-7.62 (m, 2H), 7.77 (d, J = 7.9 Hz, 1H), 7.87-7.90 (m, 3H), 8.18 (d, J = 7.5 Hz, 1H), 8.47 (s, 1H), 8.73 (d, J = 3.1 Hz, 1H), 8.85 (dd, J 1 = 6.2 Hz, J 2 = 2.6 Hz, 1H), 10.13 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.6, 117.1, 121.8, 122.6, 126.8 (q, 3 J C-F = 3.7 Hz), 127.3, 127.9, 128.6, 129.6, 129.8, 130.2 (q, 3 J C-F = 3.4 Hz), 132.6 (q, 2 J C-F = 33.8 Hz), 134.1, 136.3, 137.0, 138.4, 140.0, 140.4, 145.0, 148.4, 164.3; HRMS (ESI) calcd for C 24 H 17 F 3 N 2 O 3 S: (M + H + ) 471.0985, found: 471.0995. 4-Methoxy-N-(quinolin-8-yl)-2-tosylbenzamide 3f 1 H NMR (400 MHz, CDCl 3 ) δ 2.29 (s, 3H), 3.91 (s, 3H), 7.13 (dd, J 1 = 8.4 Hz, J 2 = 2.4 Hz, 1H), 7.17 (d, J = 8.1 Hz, 2H), 7.43 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.55-7.61 (m, 3H), 7.73 (d, J = 2.4 Hz, 1H), 7.84 (d, J = 8.1 Hz, 2H), 8.16 (d, J = 7.7 Hz, 1H), 8.72 (d, J = 3.3 Hz, 1H), 8.83 (d, J = 6.5 Hz, 1H), 10.04 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 55.9, 114.6, 116.9, 118.7, 121.6, 122.1, 127.3, 127.9, 128.3, 129.5, 129.6, 130.5, 134.5, 136.2, 137.9, 138.4, 140.4, 144.2, 148.3, 160.6, 165.5; HRMS (ESI) calcd for C 24 H 20 N 2 O 4 S: (M + H + ) 433.1217, found: 433.1228. N-(Quinolin-8-yl)-2-tosyl-1-naphthamide 3g 1 H NMR (400 MHz, CDCl 3 ) δ 2.31 (s, 3H), 7.19 (d, J = 8.1 Hz, 2H), 7.41 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.53-7.57 (m, 1H), 7.60-7.64 (m, 2H), 7.66-7.70 (m, 1H), 7.90 (d, J = 8.1 Hz, 1H), 7.95 (d, J = 8.2 Hz, 2H), 8.05 (dd, J 1 = 26.4 Hz, J 2 = 8.8 Hz, 2H), 8.12 (d, J = 8.5 Hz, 1H), 8.17 (dd, J 1 = 8.2 Hz, J 2 = 1.2 Hz, 1H), 8.63 (dd, J 1 = 4.1 Hz, J 2 = 1.3 Hz, 1H), 9.12 (d, J = 7.3 Hz, 1H), 10.16 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 117.1, 121.7, S6

122.3, 123.9, 126.7, 127.5, 128.0, 128.1, 128.2, 128.5, 129.2, 129.7, 130.1, 130.5, 134.4, 135.1, 135.2, 135.7, 136.2, 138.4, 144.3, 148.2, 165.1; HRMS (ESI) calcd for C 27 H 20 N 2 O 3 S: (M + H + ) 453.1267, found: 453.1259. 2-(Phenylsulfonyl)-N-(quinolin-8-yl)benzamide 3h 1 H NMR (400 MHz, CDCl 3 ) δ 7.41-7.47 (m, 3H), 7.49-7.53 (m, 1H), 7.58-7.62 (m, 2H), 7.64-7.70 (m, 3H), 8.01 (d, J = 7.9 Hz, 2H), 8.19 (d, J = 8.2 Hz, 1H), 8.23 (d, J = 7.7 Hz, 1H), 8.74 (d, J = 4.0 Hz, 1H), 8.87 (d, J = 6.8 Hz, 1H), 10.09 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 117.0, 121.7, 122.3, 127.3, 127.9, 128.3, 128.8, 128.9, 129.9, 130.3, 133.3, 133.6, 134.3, 136.3, 137.2, 138.5, 138.7, 141.0, 148.3, 165.6; HRMS (ESI) calcd for C 22 H 16 N 2 O 3 S: (M + H + ) 389.0954, found: 389.0937. 2-((4-Methoxyphenyl)sulfonyl)-N-(quinolin-8-yl)benzamide 3i 1 H NMR (400 MHz, CDCl 3 ) δ 3.75 (s, 3H), 6.86 (d, J = 8.9 Hz, 2H), 7.45 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.59-7.65 (m, 5H), 7.93 (d, J = 8.9 Hz, 2H), 8.17-8.22 (m, 2H), 8.73 (dd, J 1 = 4.0 Hz, J 2 = 1.2 Hz, 1H), 8.89 (dd, J 1 = 7.1 Hz, J 2 = 1.4 Hz, 1H), 10.04 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 55.5, 114.2, 117.0, 121.7, 122.2, 127.3, 127.9, 128.7, 129.5, 130.3, 130.7, 132.4, 133.3, 134.4, 136.3, 136.9, 138.4, 139.4, 148.3, 163.4, 165.8; HRMS (ESI) calcd for C 23 H 18 N 2 O 4 S: (M + H + ) 419.1060, found: 419.1065. S7

2-((4-(tert-Butyl)phenyl)sulfonyl)-N-(quinolin-8-yl)benzamide 3j 1 H NMR (400 MHz, CDCl 3 ) δ 1.25 (s, 9H), 7.42-7.46 (m, 3H), 7.58-7.67 (m, 5H), 7.93 (d, J = 8.5 Hz, 2H), 8.18 (dd, J 1 = 8.2 Hz, J 2 = 1.1 Hz, 1H), 8.22 (d, J = 7.7 Hz, 1H), 8.74 (dd, J 1 = 4.0 Hz, J 2 = 1.1 Hz, 1H), 8.88 (dd, J 1 = 7.0 Hz, J 2 = 1.5 Hz, 1H), 10.07 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 30.9, 35.1, 117.1, 121.7, 122.2, 126.0, 127.3, 127.9, 128.3, 128.7, 129.7, 130.3, 133.4, 134.4, 136.3, 137.1, 137.8, 138.5, 139.1, 148.3, 157.1, 165.7; HRMS (ESI) calcd for C 26 H 24 N 2 O 3 S: (M + H + ) 445.1580, found: 445.1582. 4-(tert-Butyl)-N-(quinolin-8-yl)-2-tosylbenzamide 3k 1 H NMR (400 MHz, CDCl 3 ) δ 1.39 (s, 9H), 2.28 (s, 3H), 7.17 (d, J = 7.9 Hz, 2H), 7.43 (dd, J 1 = 8.1 Hz, J 2 = 4.1 Hz, 1H), 7.56-7.62 (m, 3H), 7.68 (d, J = 7.9 Hz, 1H), 7.84 (d, J = 7.8 Hz, 2H), 8.17 (d, J = 8.2 Hz, 1H), 8.25 (s, 1H), 8.72 (d, J = 4.1 Hz, 1H), 8.85 (d, J = 7.1 Hz, 1H), 10.03 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 31.0, 35.2, 116.9, 121.6, 122.1, 126.4, 127.3, 127.9, 128.3, 128.7, 129.5, 130.4, 134.4, 134.4, 136.2, 138.1, 138.4, 138.6, 144.1, 148.3, 154.1, 165.8; HRMS (ESI) calcd for C 27 H 26 N 2 O 3 S: (M + H + ) 459.1737, found: 459.1740. 4-Fluoro-N-(quinolin-8-yl)-2-tosylbenzamide 3l 1 H NMR (400 MHz, CDCl 3 ) δ 2.31 (s, 3H), 7.19-7.22 (m, 2H), 7.32-7.37 (m, 1H), 7.45 (dd, J 1 = 8.3 Hz, J 2 = 4.2 Hz, 1H), 7.58-7.66 (m, 3H), 7.86 (d, J = 8.3 Hz, 2H), 7.92 (dd, J 1 = 8.3 Hz, J 2 = 2.6 Hz, 1H), 8.18 (dd, J 1 = 8.3 Hz, J 2 = 1.6 Hz, 1H), 8.74 (dd, J 1 = 4.2 Hz, J 2 S8

= 1.6 Hz, 1H), 8.84 (dd, J 1 = 6.7 Hz, J 2 = 2.2 Hz, 1H), 10.06 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.6, 117.0, 117.0 (d, 2 J C-F = 24.9 Hz), 120.4 (d, 2 J C-F = 21.4 Hz), 121.7, 122.4, 127.3, 127.9, 128.5, 129.7, 131.0 (d, 3 J C-F = 7.8 Hz), 133.3, 134.2, 136.3, 137.2, 138.4, 141.6, 144.7, 148.3, 162.6 (d, 1 J C-F = 255.1 Hz), 164.7; HRMS (ESI) calcd for C 23 H 17 FN 2 O 3 S: (M + H + ) 421.1017, found: 421.1019. (E)-4-fluoro-N-(5-(p-tolyldiazenyl)quinolin-8-yl)-2-tosylbenzamide 3l 1 H NMR (400 MHz, CDCl 3 ) δ 2.31 (s, 3H), 2.47 (s, 3H), 7.22 (d, J = 7.9 Hz, 2H), 7.36 (d, J = 7.6 Hz, 3H), 7.60 (dd, J 1 = 8.4 Hz, J 2 = 4.0 Hz, 1H), 7.67 (dd, J 1 = 8.1 Hz, J 2 = 5.1 Hz, 1H), 7.85 (d, J = 8.0 Hz, 2H), 7.95 (d, J = 7.9 Hz, 3H), 8.06 (d, J = 8.5 Hz, 1H), 8.81 (d, J = 2.8 Hz, 1H), 8.93 (d, J = 8.5 Hz, 1H), 9.32 (d, J = 8.2 Hz, 1H), 10.23 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 113.7, 116.5, 117.1 (d, 2 J C-F = 24.8 Hz), 120.4 (d, 2 J C-F = 21.5 Hz), 122.4, 123.1, 126.6, 128.5, 129.8 (d, 3 J C-F = 8.3 Hz), 131.1 (d, 3 J C-F = 7.7 Hz), 132.8, 133.1, 136.7, 137.2, 138.2, 141.7, 141.8, 142.6, 144.8, 148.8, 151.3, 162.7 (d, 1 J C-F = 255.1 Hz), 164.7; HRMS (ESI) calcd for C 30 H 23 FN 4 O 3 S: (M + H + ) 539.1548, found: 539.1553. 4-Chloro-N-(quinolin-8-yl)-2-tosylbenzamide 3m 1 H NMR (400 MHz, CDCl 3 ) δ 2.32 (s, 3H), 7.21 (d, J = 8.1 Hz, 2H), 7.45 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.56-7.63 (m, 4H), 7.87 (d, J = 8.2 Hz, 2H), 8.17-8.19 (m, 2H), 8.73 (d, J = 3.1 Hz, 1H), 8.84 (dd, J 1 = 6.5 Hz, J 2 = 2.1 Hz, 1H), 10.07 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.6, 117.0, 121.7, 122.4, 127.3, 127.9, 128.6, 129.6, 129.7, 130.2, 133.4, 134.2, 135.3, 136.3, 136.4, 137.3, 138.4, 140.8, 144.7, 148.4, 164.6; HRMS (ESI) calcd for C 23 H 17 ClN 2 O 3 S: (M + H + ) 437.0721, found: 437.0717. S9

(E)-4-chloro-N-(5-(p-tolyldiazenyl)quinolin-8-yl)-2-tosylbenzamide 3m 1 H NMR (400 MHz, CDCl 3 ) δ 2.32 (s, 3H), 2.47 (s, 3H), 7.22 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.59-7.64 (m, 3H), 7.86 (d, J = 8.1 Hz, 2H), 7.95 (d, J = 8.1 Hz, 2H), 8.07 (d, J = 8.5 Hz, 1H), 8.22 (d, J = 1.1 Hz, 1H), 8.82 (d, J = 2.8 Hz, 1H), 8.93 (d, J = 8.5 Hz, 1H), 9.33 (d, J = 7.6 Hz, 1H), 10.24 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 113.7, 116.5, 122.4, 123.1, 126.5, 128.5, 129.6, 129.7, 129.8, 130.2, 132.8, 133.4, 135.1, 136.6, 137.2, 138.2, 140.9, 141.8, 142.7, 144.8, 148.8, 151.3, 164.7; HRMS (ESI) calcd for C 30 H 23 ClN 4 O 3 S: (M + H + ) 555.1252, found: 555.1243. 4-Bromo-N-(quinolin-8-yl)-2-tosylbenzamide 3n 1 H NMR (400 MHz, CDCl 3 ) δ 2.31 (s, 3H), 7.21 (d, J = 8.1 Hz, 2H), 7.44 (dd, J 1 = 8.2 Hz, J 2 = 4.2 Hz, 1H), 7.49 (d, J = 8.1 Hz, 1H), 7.57-7.62 (m, 2H), 7.75 (dd, J 1 = 8.1 Hz, J 2 = 1.5 Hz, 1H), 7.86 (d, J = 8.2 Hz, 2H), 8.17 (d, J = 8.2 Hz, 1H), 8.33 (d, J = 1.5 Hz, 1H), 8.72 (d, J = 3.1 Hz, 1H), 8.84 (dd, J 1 = 6.5 Hz, J 2 = 2.1 Hz, 1H), 10.07 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.6, 117.0, 121.8, 122.4, 124.2, 127.3, 127.9, 128.6, 129.6, 130.2, 132.4, 134.2, 135.7, 136.3, 136.4, 137.3, 138.4, 140.8, 144.7, 148.4, 164.7; HRMS (ESI) calcd for C 23 H 17 BrN 2 O 3 S: (M + H + ) 481.0216, found: 481.0211. (E)-4-Bromo-N-(5-(p-tolyldiazenyl)quinolin-8-yl)-2-tosylbenzamide 3n 1 H NMR (400 MHz, CDCl 3 ) δ 2.32 (s, 3H), 2.47 (s, 3H), 7.22 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 8.1 Hz, 2H), 7.53 (d, J = 8.1 Hz, 1H), 7.61 (dd, J 1 = 8.5 Hz, J 2 = 4.2 Hz, 1H), 7.79 (dd, S10

J 1 = 8.1 Hz, J 2 = 1.8 Hz, 1H), 7.86 (d, J = 8.2 Hz, 2H), 7.95 (d, J = 8.2 Hz, 2H), 8.07 (d, J = 8.5 Hz, 1H), 8.37 (d, J = 1.8 Hz, 1H), 8.81 (dd, J 1 = 4.0 Hz, J 2 = 1.4 Hz, 1H), 8.92 (d, J = 8.5 Hz, 1H), 9.33 (dd, J 1 = 8.5 Hz, J 2 = 1.4 Hz, 1H), 10.23 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 113.7, 116.5, 122.4, 123.1, 124.4, 126.5, 128.5, 129.7, 129.8, 130.2, 132.4, 132.8, 135.5, 136.4, 136.6, 137.2, 138.2, 140.9, 141.8, 142.7, 144.8, 148.8, 151.3, 164.7; HRMS (ESI) calcd for C 30 H 23 BrN 4 O 3 S: (M + H + ) 599.0747, found: 599.0751. 2-((4-Fluorophenyl)sulfonyl)-N-(quinolin-8-yl)benzamide 3o 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.42 (t, J = 8.8 Hz, 2H), 7.66 (dd, J 1 = 8.3 Hz, J 2 = 4.2 Hz, 1H), 7.70 (t, J = 7.9 Hz, 1H), 7.78-7.86 (m, 4H), 8.07-8.10 (m, 2H), 8.22 (d, J = 8.0 Hz, 1H), 8.47 (dd, J 1 = 8.3 Hz, J 2 = 1.5 Hz, 1H), 8.71 (d, J = 7.5 Hz, 1H), 8.87 (dd, J 1 = 4.1 Hz, J 2 = 1.5 Hz, 1H), 10.30 (s, 1H); 13 C NMR (100 MHz, DMSO-d 6 ) δ 117.0 (d, 2 J C-F = 22.9 Hz), 117.8, 122.7, 123.2, 127.4, 128.3, 129.2, 130.3, 131.3, 131.6 (d, 3 J C-F = 10.0 Hz), 134.6, 134.8, 137.0, 137.1, 137.8 (d, 4 J C-F = 2.9 Hz), 138.0, 138.6, 149.6, 165.3 (d, 1 J C-F = 253.1 Hz), 166.0; HRMS (ESI) calcd for C 22 H 15 FN 2 O 3 S: (M + H + ) 407.0860, found: 407.0867. (E)-N-(5-((4-Fluorophenyl)diazenyl)quinolin-8-yl)-2-((4-fluorophenyl)sulfonyl)benzam ide 3o S11

1 H NMR (400 MHz, CDCl 3 ) δ 7.12 (t, J = 8.5 Hz, 2H), 7.25 (dd, J 1 = 10.5 Hz, J 2 = 6.4 Hz, 2H), 7.63 (dd, J 1 = 8.5 Hz, J 2 = 4.1 Hz, 1H), 7.67-7.73 (m, 3H), 8.04-8.10 (m, 5H), 8.24 (d, J = 7.6 Hz, 1H), 8.83 (d, J = 2.9 Hz, 1H), 8.98 (d, J = 8.5 Hz, 1H), 9.31 (d, J = 8.1 Hz, 1H), 10.28 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 113.9, 116.2 (d, 2 J C-F = 22.9 Hz), 116.3 (d, 2 J C-F = 22.8 Hz), 116.4, 122.6, 125.0 (d, 3 J C-F = 8.8 Hz), 126.6, 128.7, 129.9, 130.6, 131.3 (d, 3 J C-F = 9.7 Hz), 132.7, 133.8, 136.9, 137.0, 137.1, 138.2, 138.7, 142.3, 148.9, 149.7, 164.4 (d, 1 J C-F = 252.4 Hz), 165.6 (d, 1 J C-F = 256.4 Hz), 165.8; HRMS (ESI) calcd for C 28 H 18 F 2 N 4 O 3 S: (M + H + ) 529.1140, found: 529.1148. 2-((4-Chlorophenyl)sulfonyl)-N-(quinolin-8-yl)benzamide 3p 1 H NMR (400 MHz, CDCl 3 ) δ 7.37 (d, J = 8.7 Hz, 2H), 7.45 (dd, J 1 = 8.3 Hz, J 2 = 4.2 Hz, 1H), 7.57-7.62 (m, 2H), 7.65-7.73 (m, 3H), 7.95 (d, J = 8.7 Hz, 2H), 8.18 (dd, J 1 = 8.3 Hz, J 2 = 1.6 Hz, 1H), 8.22-8.24 (m, 1H), 8.73 (dd, J 1 = 4.2 Hz, J 2 = 1.6 Hz, 1H), 8.87 (dd, J 1 = 7.0 Hz, J 2 = 1.9 Hz, 1H), 10.04 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 116.9, 121.8, 122.4, 127.3, 127.9, 128.8, 129.2, 129.8, 129.9, 130.5, 133.9, 134.2, 136.3, 137.3, 138.4, 139.6, 139.9, 148.4, 165.5; HRMS (ESI) calcd for C 22 H 15 ClN 2 O 3 S: (M + H + ) 423.0565, found: 423.0566. (E)-N-(5-((4-Chlorophenyl)diazenyl)quinolin-8-yl)-2-((4-chlorophenyl)sulfonyl)benzam ide 3p S12

1 H NMR (400 MHz, CDCl 3 ) δ 7.40 (d, J = 8.2 Hz, 2H), 7.53 (d, J = 8.3 Hz, 2H), 7.63 (dd, J 1 = 8.5 Hz, J 2 = 4.0 Hz, 1H), 7.70-7.74 (m, 3H), 7.95-7.99 (m, 4H), 8.10 (d, J = 8.5 Hz, 1H), 8.25 (d, J = 8.0 Hz, 1H), 8.82 (d, J = 3.9 Hz, 1H), 8.98 (d, J = 8.5 Hz, 1H), 9.31 (d, J = 8.5 Hz, 1H), 10.24 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 114.1, 116.4, 122.7, 124.3, 126.7, 128.7, 129.3, 129.4, 129.8, 130.0, 130.7, 132.7, 133.9, 136.9, 137.3, 138.1, 138.4, 139.5, 140.1, 142.3, 148.9, 151.4, 165.7; HRMS (ESI) calcd for C 28 H 18 Cl 2 N 4 O 3 S: (M + H + ) 561.0549, found: 561.0565. 2-((4-Bromophenyl)sulfonyl)-N-(quinolin-8-yl)benzamide 3q 1 H NMR (400 MHz, CDCl 3 ) δ 7.44 (dd, J 1 = 8.3 Hz, J 2 = 4.2 Hz, 1H), 7.53 (d, J = 8.7 Hz, 2H), 7.59-7.61 (m, 2H), 7.64-7.69 (m, 3H), 7.87 (d, J = 8.7 Hz, 2H), 8.17 (dd, J 1 = 8.3 Hz, J 2 = 1.6 Hz, 1H), 8.22 (d, J = 7.8 Hz, 1H), 8.71 (dd, J 1 = 4.2 Hz, J 2 = 1.6 Hz, 1H), 8.87 (dd, J 1 = 7.0 Hz, J 2 = 1.8 Hz, 1H), 10.04 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 116.9, 121.8, 122.4, 127.3, 127.9, 128.6, 128.8, 129.8, 129.9, 130.5, 132.2, 133.9, 134.2, 136.3, 137.3, 138.2, 138.3, 140.1, 148.4, 165.5; HRMS (ESI) calcd for C 22 H 15 BrN 2 O 3 S: (M + H + ) 467.0060, found: 467.0067. (E)-N-(5-((4-Bromophenyl)diazenyl)quinolin-8-yl)-2-((4-bromophenyl)sulfonyl)benza mide 3q 1 H NMR (400 MHz, CDCl 3 ) δ 7.57 (d, J = 8.4 Hz, 2H), 7.64 (dd, J 1 = 8.5 Hz, J 2 = 4.1 Hz, S13

1H), 7.69-7.75 (m, 5H), 7.88 (d, J = 8.4 Hz, 2H), 7.92 (d, J = 8.5 Hz, 2H), 8.11 (d, J = 8.5 Hz, 1H), 8.25 (d, J = 8.1 Hz, 1H), 8.83 (d, J = 4.0 Hz, 1H), 8.98 (d, J = 8.6 Hz, 1H), 9.32 (d, J = 8.5 Hz, 1H), 10.24 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 114.2, 116.4, 122.7, 124.5, 125.5, 126.7, 128.7, 128.8, 129.9, 130.1, 130.7, 132.3, 132.4, 132.7, 133.9, 136.9, 137.3, 138.1, 138.4, 140.0, 142.3, 148.9, 151.8, 165.7; HRMS (ESI) calcd for C 28 H 18 Br 2 N 4 O 3 S: (M + H + ) 648.9539, found: 648.9532. (E)-N-(5-((3-Chlorophenyl)diazenyl)quinolin-8-yl)-2-((3-chlorophenyl)sulfonyl)benzam ide 3r 1 H NMR (400 MHz, CDCl 3 ) δ 7.40 (t, J = 7.9 Hz, 1H), 7.47-7.54 (m, 3H), 7.65 (dd, J 1 = 8.4 Hz, J 2 = 4.1 Hz, 1H), 7.70-7.76 (m, 3H), 7.92-7.97 (m, 2H), 7.99 (d, J = 8.6 Hz, 2H), 8.12 (d, J = 8.5 Hz, 1H), 8.26 (d, J = 7.5 Hz, 1H), 8.83 (d, J = 3.7 Hz, 1H), 8.99 (d, J = 8.5 Hz, 1H), 9.34 (d, J = 8.5 Hz, 1H), 10.27 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 114.4, 116.4, 121.5, 122.8, 122.9, 126.5, 126.8, 128.3, 128.8, 130.1, 130.2, 130.3, 130.7, 132.7, 133.5, 134.1, 135.1, 135.2, 137.0, 137.5, 138.1, 138.1, 142.2, 142.7, 148.9, 153.8, 165.6; HRMS (ESI) calcd for C 28 H 18 Cl 2 N 4 O 3 S: (M + H + ) 561.0549, found: 561.0558. Methyl (E)-3-((2-((5-((3-(methoxycarbonyl)phenyl)diazenyl)quinolin-8-yl)carbamoyl)phenyl)s S14

ulfonyl)benzoate 3s 1 H NMR (400 MHz, CDCl 3 ) δ 3.83 (s, 3H), 4.01 (s, 3H), 7.55 (t, J = 7.8 Hz, 1H), 7.63-7.67 (m, 2H), 7.70-7.76 (m, 3H), 8.12 (d, J = 8.5 Hz, 1H), 8.16-8.23 (m, 4H), 8.33 (d, J = 8.2 Hz, 1H), 8.59 (s, 1H), 8.67 (s, 1H), 8.81 (d, J = 2.9 Hz, 1H), 8.96 (d, J = 8.5 Hz, 1H), 9.36 (d, J = 7.6 Hz, 1H), 10.25 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 52.4, 52.5, 114.3, 116.4, 122.8, 123.9, 126.7, 127.3, 128.8, 129.2, 129.3, 130.1, 130.7, 131.1, 131.4, 131.7, 132.5, 132.7, 134.1, 134.2, 136.9, 137.4, 138.1, 138.2, 141.6, 142.3, 148.9, 152.9, 165.2, 165.5, 166.6; HRMS (ESI) calcd for C 32 H 24 N 4 O 7 S: (M + H + ) 609.1438, found: 609.1425. References: 1. J. Liu, L. Yu, S. Zhuang, Q. Gui, X. Chen, W. Wang, Z. Tan, Chem. Commun., 2015, 51, 16928. S15