The Suzuki Miyaura Coupling of Nitroarenes

Transcription

1 Supporting Information for the Communication: The Suzuki Miyaura Coupling of Nitroarenes M. Ramu Yadav, Masahiro Nagaoka, Myuto Kashiahra, Rong-Lin Zhong, Takanori Miyazaki, Shigeyoshi Sakaki,,* Yoshiaki Nakao,* Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto , Japan Fukui Institute for Fundamental Chemistry, Kyoto University, Sakyo-ku, Kyoto , Japan Tosoh Corporation, 4560 Kaisei-cho, Shunan-shi, Yamaguchi , Japan Table of Contents Page 1. General information S2 2. Optimization studies S3 3. Substrate scope studies S4 4. Control experiments S15 5. Stoichiometric reactions S16 6. Sequential Functionalization of Nitroarenes S19 7. Competitive Reaction S22 8. X-ray diffraction studies S23 9. Ion chromatography S Computational details S References S NMR and IR spectra S59 S1

2 1. General information All manipulations of oxygen- and moisture-sensitive materials were conducted with a standard Schlenk technique under an argon atmosphere or in a glove box under a nitrogen atmosphere. Medium pressure liquid chromatography (MPLC) was performed using Kanto Chemical silica gel 60 (spherical, m) or Biotage SNAP Ultra. Analytical thin layer chromatography (TLC) was performed on Merck TLC silica gel 60 F254 (0.25 mm) plates. Visualization was accomplished with UV light (254 nm) and/or an aqueous alkaline KMnO4 solution followed by heating. Proton, boron, carbon, fluorine, and phosphorus nuclear magnetic resonance spectra ( 1 H, 11 B, 13 C, 19 F, and 31 P NMR) were recorded on a JEOL ECS-400 ( 1 H NMR, 400 MHz; 11 B NMR, 128 MHz; 13 C NMR, 101 MHz; 19 F NMR, 376 MHz; 31 P NMR, 162 MHz) spectrometer with solvent resonance as the internal standard ( 1 H NMR, CDCl3 at 7.26 ppm, C6D6 at 7.16 ppm, THF-d8 at 3.58 ppm; 13 C NMR, CDCl3 at 77.0 ppm, C6D6 at ppm). In the 11 B and 19 F NMR, Et2O BF3 (at 0.0 ppm) and C6F6 (at ppm) were used as the external standard, respectively. In the case of 31 P NMR, the capillary sealing H3PO4 (85wt% in H2O, diluted 100-fold by D2O) was used as an external standard (at 0.70 ppm). NMR data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, sept = septet, m = multiplet), coupling constants (Hz), and integration. Highresolution mass spectra were obtained with Thermo Scientific Exactive (ESI or APCI) and Thermo Scientific TM MALDI LTQ Orbitrap (MALDI). GC analysis was performed on a Shimadzu GC-2014 equipped with a BP1 column (SGE Analytical Science, 0.25 mm 30 m, pressure = kpa, detector = FID, 290 C) with helium gas as a carrier. Medium pressure liquid chromatography (MPLC) was performed with a Yamazen EPLC-W-Prep 2XY or SHOKO SCIENTIFIC Purif-espoir2. The IR spectra were recorded on a SHIMADZU IRAffinity-1. Elemental analyses were performed on a J-Science Microcorder JM10. All the commercially available starting materials i.e. nitroarenes, arylboronic acid derivatives, bases, and additives were used without further purification. The Pd(acac)2 catalyst and BrettPhos ligand were purchased from Aldrich. K3PO4 nh2o was purchased from nacalai tesque, and anhydrous K3PO4 was prepared from K3PO4 nh2o by heating at 160 ºC under reduced pressure for 5 h. Both potassium phosphate bases employed in this study were analyzed by TG-DTA measurement, and the actual water contents of K3PO4 nh2o and anhydrous K3PO4 were 11 wt% and 1 wt%, respectively. The averaged particle sizes of K3PO4 nh2o and anhydrous K3PO4 were 30 m and 28 m estimated from the microscopic observations. (cod)pd(ch2sime3)2 was prepared according to the previously published method. 1 All the anhydrous solvents (THF, toluene, 1,4-dioxane, pentane, DMSO, and DMF) were purchased from Wako Pure Chemical Industries. Anhydrous hexane was purchased from Kanto Chemical and degassed by purging vigorously with argon for 30 min and further purified by passage through activated alumina under positive argon pressure as described by Grubbs et al. 2 C6D6 was purchased from Aldrich and dried over sodiumbenzophenone ketyl. THF-d8 was purchased from Aldrich and degassed via 3 freeze-pump-thaw cycles followed by drying over MS-4A. S2

3 2. Optimization studies General procedure for optimization studies. A 15-mL Iwaki screw caped vial was charged with 4- nitroanisole 1a (46 mg, 0.30 mmol), phenylboronic acid 2a (55 mg, 0.45 mmol), catalyst (5.0 mol%), ligand (20 mol%), and base (0.90 mmol). Subsequently, 1,4-dioxane (1.5 ml) was introduced into the vial in a glove box under N2 atmosphere and the vial was taken outside. The reaction mixture was stirred at 130 C. After 24 h, it was allowed to cool to room temperature. The reaction mixture was passed through a short pad of celite with CH2Cl2 and the solution was concentrated in vacuo. The yield of the product was determined by NMR analysis using 1,3,5-trimethoxybenzene as an internal standard. Table S1. Optimization of the SMC of 4-nitroanisole. Entry Variation from the standard conditions Yield of 3 (%) a 1 none 86 (76) b 2 w/o 18-crown SPhos instead of BrettPhos 8 4 RuPhos instead of BrettPhos 15 5 CPhos instead of BrettPhos 9 6 XPhos instead of BrettPhos 56 7 PCy3 instead of BrettPhos <5 8 P t Bu3 instead of BrettPhos <5 9 IPr instead of BrettPhos <5 10 Pd(OAc)2 instead of Pd(acac) Pd(PPh3)4 instead of Pd(acac)2 <5 12 Pd2(dba)3 instead of Pd(acac) PEPPSI -IPr instead of Pd(acac) c BrettPhos Pd G3 instead of Pd(acac) d K3PO4 instead of K3PO4 nh2o K3PO4 + H2O instead of K3PO4 nh2o K3PO4 + 2H2O instead of K3PO4 nh2o d K2CO3 instead of K3PO4 nh2o <5 19 d Cs2CO3 instead of K3PO4 nh2o d CsF instead of K3PO4 nh2o Pd(OAc)2 and CsF instead of Pd(acac)2 and K3PO4 nh2o c BrettPhos Pd G3 and CsF instead of Pd(acac)2 and K3PO4 nh2o toluene instead of 1,4-dioxane THF instead of 1,4-dioxane addition of carbazole (5.0 mol%) addition of LiCl (20 mol%) 67 a Determined by NMR analysis using 1,3,5-trimethoxybenzene as an internal standard; b isolated yield obtained from using 1a (0.60 mmol), 2a (0.90 mmol) and K3PO4 nh2o (1.8 mmol); c using BrettPhos (15 mol%); d in the absence of 18-crown-6. S3

4 3. Substrate scope studies General procedure for substrate scope. A 15-mL Iwaki screw caped vial was charged with nitroarene (0.60 mmol), arylboronic acid ( mmol), Pd(acac)2 (9.1 mg, mmol), BrettPhos (64 mg, mmol), K3PO4 nh2o (0.48 g, 1.80 mmol) and 18-crown-6 (16 mg, mmol). Subsequently, 1,4-dioxane (3.0 ml) was introduced into the vial in a glove box under N2 atmosphere and the vial was taken outside (liquid nitrobenzene derivatives were added in glove box). The reaction mixture was stirred at 130 C for h. The unreacted nitroarene starting material was determined by GC analysis of the crude mixture. After completion of the reaction, it was allowed to cool to room temperature. The reaction mixture was passed through a short pad of celite with CH2Cl2 and the solution was concentrated in vacuo. The residue was purified by MPLC on silica gel to give the corresponding biaryl products. The purification of mixture of the biaryl products with BrettPhos ligand was done through oxidation procedure followed by MPLC on silica gel. General procedure for oxidation of BrettPhos. 3 The crude reaction mixture obtained after celite filtration was diluted with Et2O or CH2Cl2 (20 ml) and subsequently 30% H2O2 (5.0 ml) was added to oxidize the phosphine ligand. The resulting mixture was stirred until complete oxidation of phosphine ligand at room temperature (5 20 min). The solution was taken into a separating funnel and aqueous layer was removed. Further, organic layer was washed with distilled water (10 ml) and saturated aqueous FeSO4 (10 ml). The combined aqueous layer was extracted with Et2O (3 20 ml). The two organic layer extracts were combined and washed with brine (10 ml). The resulting solution was dried over anhydrous magnesium sulfate, and concentrated in vacuo. The crude residue was purified by MPLC on silica gel to give the corresponding biaryl products. 4-Methoxy-1,1'-biphenyl (3). The reaction of 4-nitroanisole 1a (92 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 24 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (84 mg, 0.46 mmol, 76%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), 7.42 (t, J = 7.4 Hz, 2H), 7.31 (t, J = 7.4 Hz, 1H), 6.99 (d, J = 8.1 Hz, 2H), 3.86 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 159.1, 140.8, 133.7, 128.7, 128.1, 126.7, 126.6, 114.2, Spectral data obtained for the compound are in good agreement with the reported data. 4 4-([1,1'-Biphenyl]-4-yl)morpholine (4). The reaction of 4-(4- nitrophenyl)morpholine 1b (125 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 24 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 75:25) gave the title compound (90 mg, 0.38 mmol, 63%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), 7.45 (t, J = 7.4 Hz, 2H), 7.33 (t, J = 7.4 Hz, 1H), 7.01 (d, J = 8.7 Hz, 2H), 3.91 (m, 4H), 3.23 (m, 4H); 13 C NMR (101 MHz, CDCl3): δ 150.5, 140.7, 132.6, 128.6, 127.7, 126.5, 115.7, 66.8, 49.1 (one 13 C value merged with other peaks). Spectral data obtained for the compound are in good agreement with the reported data. 5 4-Methoxy-4'-methyl-1,1'-biphenyl (5). The reaction of 4- nitrotoluene 1c (82 mg, 0.60 mmol) and 4-methoxyphenylboronic acid 2b (137 mg, 0.90 mmol) with optimized condition stirred for 24 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purifespoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (93 mg, 0.47 mmol, 78%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ S4

5 7.52 (d, J = 8.7 Hz, 2H), 7.46 (d, J = 7.4 Hz, 2H), 7.23 (d, J = 8.1 Hz, 2H), 6.97 (d, J = 8.1 Hz, 2H), 3.85 (s, 3H), 2.39 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 158.9, 137.9, 136.3, 133.7, 129.4, 127.9, 126.5, 114.1, 55.2, Spectral data obtained for the compound are in good agreement with the reported data. 6 1,1':4',1''-Terphenyl (6). The reaction of 4-nitrobiphenyl 1d (119 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 16 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (98 mg, 0.42 mmol, 71%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 8H), 7.47 (t, J = 7.5 Hz, 4H), 7.37 (t, J = 7.3 Hz, 2H); 13 C NMR (101 MHz, CDCl3): δ 140.7, 140.1, 128.8, 127.5, 127.3, Spectral data obtained for the compound are in good agreement with the reported data. 7 4-Methoxy-1,1'-biphenyl (3). The reaction of nitrobenzene 1e (74 mg, 62 L, 0.60 mmol) and 4-methoxyphenylboronic acid 2b (137 mg, 0.90 mmol) with optimized condition stirred for 12 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (80 mg, 0.43 mmol, 72%) as a white solid. Spectral data obtained for the compound are in agreement with the reported data. 4 [1,1'-Biphenyl]-4-carbaldehyde (7). The reaction of 2-(4-nitrophenyl)-1,3- dioxolane 1f (117 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to hydrolysis (3N HCl (3.0 ml) and 2-propanol (10 ml) at 80 C for 3 h) and oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (77 mg, 0.42 mmol, 70%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (s, 1H, CHO), 7.96 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.65 (d, J = 8.2 Hz, 2H), 7.49 (t, J = 7.3 Hz, 2H), 7.42 (t, J = 7.3 Hz, 1H); 13 C NMR (101 MHz, CDCl3): δ 191.8, 147.0, 139.6, 135.1, 130.2, 128.9, 128.4, 127.6, Spectral data obtained for the compound are in good agreement with the reported data. 8 1-([1,1'-Biphenyl]-4-yl)ethan-1-one (8). The reaction of 2-methyl-2-(4- nitrophenyl)-1,3-dioxolane 1g (125 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to hydrolysis (3N HCl (3.0 ml) and 2-propanol (10 ml) at 80 C for 3 h) and oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 92:8) gave the title compound (85 mg, 0.43 mmol, 72%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.04 (d, J = 8.1 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.63 (d, J = 8.1 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.41 (t, J = 7.4 Hz, 1H), 2.64 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 197.7, 145.7, 139.8, 135.7, 128.9, 128.8, 128.2, 127.2, 127.1, Spectral data obtained for the compound are in good agreement with the reported data. 9 4-Methoxy-4'-(trifluoromethyl)-1,1'-biphenyl (9). The reaction of 1- nitro-4-(trifluoromethyl)benzene 1h (115 mg, 0.60 mmol) and 4- methoxyphenylboronic acid 2b (182 mg, 1.20 mmol) with optimized condition [base replaced with CsF (0.27 g, 1.80 mmol) in toluene (3.0 ml) and without 18-crown-6 additive] stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by S5

6 purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 96:4 ) gave the title compound (82 mg, 0.32 mmol, 54%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), 7.56 (d, J = 8.7 Hz, 2H), 7.02 (d, J = 8.7 Hz, 2H), 3.88 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 159.8, 144.2, 132.1, (q, J = 32.6 Hz), 128.3, 126.8, (q, J = 3.8 Hz), (q, J = 272 Hz), 114.4, 55.3; 19 F NMR (376 MHz, CDCl3): δ Spectral data obtained for the compound are in agreement with the data reported ( 13 C peak at is quartet, in spectra it is merged with other peaks). 6 4-Fluoro-4'-methoxy-1,1'-biphenyl (10). The reaction of 1-fluoro-4- nitrobenzene 1i (85 mg, 0.60 mmol) and 4-methoxyphenylboronic acid 2b (137 mg, 0.90 mmol) with optimized condition [base replaced with CsF (0.46 g, 3.0 mmol) in toluene (3.0 ml) and without 18-crown-6 additive] stirred for 15 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (56 mg, 0.28 mmol, 46%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), (m, 2H), (m, 2H), 3.86 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ (d, J = Hz), 159.1, (d, J = 3.8 Hz), 132.8, (d, J = 8.6 Hz), 128.0, (d, J = 21.1 Hz), 114.2, 55.3; 19 F NMR (376 MHz, CDCl3): δ Spectral data obtained for the compound are in good agreement with the reported data. 6 3-Methoxy-1,1'-biphenyl (11). The reaction of 3-nitroanisole 1j (92 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 18 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (82 mg, 0.45 mmol, 74%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 8.1 Hz, 2H), 7.46 (t, J = 7.4 Hz, 2H), (m, 2H), 7.20 (d, J = 7.4 Hz, 1H), 7.15 (s, 1H), 6.92 (d, J = 7.4 Hz, 1H), 3.88 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 159.9, 142.8, 141.1, 129.7, 128.7, 127.4, 127.2, 119.7, 112.9, 112.6, Spectral data obtained for the compound are in good agreement with the reported data. 10 4'-Methoxy-3,5-dimethyl-1,1'-biphenyl (12). The reaction of 1,3- dimethyl-5-nitrobenzene 1k (91 mg, 0.60 mmol) and 4- methoxyphenylboronic acid 2b (182 mg, 1.20 mmol) with optimized condition stirred for 24 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (90 mg, 0.42 mmol, 71%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 7.52 (d, J = 8.7 Hz, 2H), 7.18 (s, 2H), (m, 3H), 3.86 (s, 3H), 2.38 (s, 6H); 13 C NMR (101 MHz, CDCl3): δ 159.0, 140.8, 138.2, 134.0, 128.3, 128.1, 124.7, 114.0, 55.3, Spectral data obtained for the compound are in good agreement with the reported data. 6 4-Methoxy-1,1':3',1''-terphenyl (13). The reaction of 3-nitro-1,1'- biphenyl 16 (119 mg, 0.60 mmol) and 4-methoxyphenylboronic acid 2b (137 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 98:2) gave the title compound (115 mg, 0.44 mmol, 74%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 7.85 (s, 1H), 7.72 (d, J = 7.4 Hz, 2H), 7.65 (d, J = 8.1 Hz, 2H), (m, 2H), (m, 3H), 7.43 (t, J = 7.4 Hz, 1H), 7.06 (d, J = 8.7 Hz, 2H), 3.90 (s, 3H); S6

7 13 C NMR (101 MHz, CDCl3): δ 159.2, 141.7, 141.3, 141.2, 133.6, 129.1, 128.7, 128.2, 127.3, 127.2, 125.7, 125.5, 114.2, 55.3 (one 13 C value is merged with other peaks). Spectral data obtained for the compound are in agreement with the reported data. 11 Methyl [1,1'-biphenyl]-3-carboxylate (14). The reaction of methyl 3- nitrobenzoate 1m (109 mg, 0.60 mmol) and phenylboronic acid 2a (146 mg, 1.20 mmol) with optimized condition stirred for 12 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC- Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (88 mg, 0.42 mmol, 69%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ 8.29 (s, 1H), 8.03 (d, J = 7.7 Hz, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.63 (d, J = 8.1 Hz, 2H), 7.52 (t, J = 7.7 Hz, 1H), 7.47 (t, J = 7.7 Hz, 2H), 7.38 (t, J = 7.0 Hz, 1H), 3.95 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 167.0, 141.4, 140.1, 131.5, 130.7, 128.9, 128.8, 128.3, 128.2, 127.7, 127.1, Spectral data obtained for the compound are in good agreement with the reported data (Methylsulfonyl)-1,1'-biphenyl (15). The reaction of 1-(methylsulfonyl)-3- nitrobenzene 1n (121 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 12 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 70:30) gave the title compound (91 mg, 0.39 mmol, 65%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.16 (s, 1H), 7.89 (dd, J = 19.5, 8.1 Hz, 2H), (m, 3H), 7.48 (t, J = 7.4 Hz, 2H), 7.42 (t, J = 7.4 Hz, 1H), 3.10 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 142.7, 141.1, 138.9, 132.2, 129.8, 129.1, 128.4, 127.2, 125.9, 125.8, Spectral data obtained for the compound are in good agreement with the reported data Nitro-1,1'-biphenyl (16). The reaction of 1,3-dinitrobenzene 1o (101 mg, 0.60 mmol) and phenylboronic acid 2a (146 mg, 1.20 mmol) with optimized condition stirred for 5 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (77 mg, 0.39 mmol, 65%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.45 (s, 1H), 8.20 (d, J = 8.1 Hz, 1H), 7.92 (d, J = 8.1 Hz, 1H), (m, 3H), 7.50 (t, J = 7.4 Hz, 2H), 7.44 (t, J = 7.4 Hz, 1H); 13 C NMR (101 MHz, CDCl3): δ 148.7, 142.8, 138.6, 133.0, 129.7, 129.1, 128.5, 127.1, 122.0, Spectral data obtained for the compound are in good agreement with the reported data Methoxy-1,1'-biphenyl (17). The reaction of 2-nitroanisole 1p (92 mg, 73 L, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 12 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (93 mg, 0.50 mmol, 84%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ (m, 2H), 7.43 (t, J = 7.4 Hz, 2H), (m, 3H), 7.05 (t, J = 7.4 Hz, 1H), 7.00 (d, J = 8.7 Hz, 1H), 3.83 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 156.4, 138.5, 130.9, 130.7, 129.5, 128.6, 128.0, 126.9, 120.8, 111.2, Spectral data obtained for the compound are in good agreement with the reported data Methoxy-2'-methyl-1,1'-biphenyl (18). The reaction of 1-methyl-2- nitrobenzene 1q (82 mg, 70 L, 0.60 mmol) and 4-methoxyphenylboronic acid 2b (137 mg, 0.90 mmol) with optimized condition stirred for 24 h. The crude reaction mixture subjected to oxidation condition followed by S7

8 purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (81 mg, 0.41 mmol, 68%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ (m, 6H), 6.97 (d, J = 8.7 Hz, 2H), 3.87 (s, 3H), 2.29 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 158.5, 141.5, 135.5, 134.3, 130.3, 130.2, 129.9, 126.9, 125.7, 113.4, 55.3, Spectral data obtained for the compound are in good agreement with the reported data Methoxy-1,1':2',1''-terphenyl (19). The reaction of 2-nitro-1,1'- biphenyl 20 (119 mg, 0.60 mmol) and 4-methoxyphenylboronic acid 2b (182 mg, 1.2 mmol) with optimized condition [RuPhos (56 mg, 0.12 mmol) was used instead of BrettPhos, base replaced with CsF (0.27 g, 1.8 mmol) and without 18-crown-6 additive] stirred for 36 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 97:3) gave the title compound (53 mg, 0.20 mmol, 34%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), (m, 5H), 7.07 (d, J = 8.7 Hz, 2H), 6.77 (d, J = 8.7 Hz, 2H), 3.79 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 158.2, 141.7, 140.4, 140.1, 133.8, 130.9, 130.6, 130.5, 129.8, 127.9, 127.4, 127.1, 126.3, 113.3, Spectral data obtained for the compound are in good agreement with the reported data Nitro-1,1'-biphenyl (20). The reaction of 1,2-dinitrobenzene 1s (101 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition [base replaced with CsF (0.27 g, 1.8 mmol) and without 18-crown-6 additive] stirred for 3 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 95:5) gave the title compound (77 mg, 0.38 mmol, 64%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 7.86 (dd, J = 8.0, 1.1 Hz, 1H), 7.62 (td, J = 7.6, 1.1 Hz, 1H), (m, 5H), (m, 2H); 13 C NMR (101 MHz, CDCl3): δ 149.2, 137.3, 136.2, 132.2, 131.9, 128.6, , , 127.8, Spectral data obtained for the compound are in good agreement with the reported data Phenylnaphthalene (21). The reaction of 1-nitronaphthalene 1t (104 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 12 h, followed by purification by MPLC-Purif-espoir 2 (10 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0) gave the title compound (101 mg, 0.49 mmol, 82%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ (m, 3H), (m, 9H); 13 C NMR (101 MHz, CDCl3): δ 140.7, 140.2, 133.8, 131.6, 130.1, 128.2, 127.6, 127.2, 126.9, 126.0, 125.7, (two 13 C values merged with other peaks). Spectral data obtained for the compound are in good agreement with the reported data. 7 S8

9 1-Nitro-5-phenylnaphthalene (22). The reaction of 1,5-dinitronaphthalene 1u (131 mg, 0.60 mmol) and phenylboronic acid 2a (146 mg, 1.20 mmol) with optimized condition stirred for 3 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (91 mg, 0.36 mmol, 61%) as a yellow solid [mp ºC (dec.)]. 1 H NMR (400 MHz, CDCl3): δ 8.52 (d, J = 8.7 Hz, 1H), 8.18 (d, J = 8.1 Hz, 2H), 7.75 (t, J = 7.7 Hz, 1H), (m, 7H); 13 C NMR (101 MHz, CDCl3): δ 147.2, 141.0, 139.7, 132.7, 132.5, 130.0, 128.7, 128.5, 128.3, 127.8, 125.4, 124.0, 123.5, 122.3; HRMS [APCI(+)] m/z calcd for C16H11NO2 [M. ] + : Found: (4-Methoxyphenyl)-5-phenylnaphthalene (23). The reaction of 1- nitro-5-phenylnaphthalene 22 (145 mg, 0.58 mmol) and 4- methoxyphenylboronic acid 2b (133 mg, 0.87 mmol) with optimized condition stirred for 18 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 97:3) gave the title compound (129 mg, 0.42 mmol, 69%) as a white solid [mp ºC (dec.)]. 1 H NMR (400 MHz, CDCl3): δ 7.94 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), (m, 11H), 7.05 (d, J = 8.7 Hz, 2H), 3.91 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 158.9, 141.0, 140.5, 140.1, 133.3, 132.2, 132.0, 131.2, 130.1, 128.2, 127.2, 126.9, 126.8, 125.8, 125.4, 125.3, 113.7, 55.3 (one 13 C value merged with other peak); HRMS [APCI(+)] m/z calcd for C23H18O [M+H] + : Found: Phenylanthracene (24). The reaction of 9-nitroanthracene 1w (134 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition [base replaced with CsF (0.27 g, 1.8 mmol) in toluene (3.0 ml) and without 18- crown-6 additive] stirred for 24 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (67 mg, 0.26 mmol, 44%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.53 (s, 1H), 8.08 (d, J = 8.1 Hz, 2H), 7.72 (d, J = 9.4 Hz, 2H), (m, 3H), (m, 4H), (m, 2H); 13 C NMR (101 MHz, CDCl3): δ 138.7, 137.0, 131.3, 131.2, 130.2, , , 127.4, 126.8, 126.5, 125.3, Spectral data obtained for the compound are in good agreement with the reported data Phenylnaphthalene (25). The reaction of 2-nitronaphthalene 1x (104 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 12 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0) gave the title compound (100 mg, 0.49 mmol, 81%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.06 (s, 1H), 7.92 (t, J = 8.7 Hz, 2H), 7.88 (d, J = 7.4 Hz, 1H), (m, 3H), (m, 4H), 7.40 (t, J = 7.0 Hz, 1H); 13 C NMR (101 MHz, CDCl3): δ 141.1, 138.5, 133.6, 132.6, 128.8, 128.4, 128.2, 127.6, 127.4, 127.3, 126.3, 125.9, 125.8, Spectral data obtained for the compound are in good agreement with the reported data. 9 3-Phenylpyridine (26). The reaction of 3-nitropyridine 1y (74 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 12 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 70:30) gave the title compound (73 mg, 0.47 mmol, 79%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): S9

10 δ 8.86 (s, 1H), 8.59 (d, J = 4.7 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 8.1 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), (m, 2H); 13 C NMR (101 MHz, CDCl3): δ 148.5, 148.3, 137.8, 136.6, 134.3, 129.0, 128.1, 127.1, Spectral data obtained for the compound are in good agreement with the reported data Methoxy-3-phenylpyridine (27). The reaction of 2-methoxy-3-nitropyridine 1z (92 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 12 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 90:10) gave the title compound (89 mg, 0.48 mmol, 80%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ 8.18 (dd, J = 4.7, 1.3 Hz, 1H), 7.62 (dd, J = 7.4, 1.3 Hz, 1H), 7.57 (d, J = 8.1 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.36 (t, J = 7.0 Hz, 1H), 6.98 (dd, J = 6.7, 4.7 Hz, 1H), 3.98 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 160.9, 145.7, 138.6, 136.7, 129.1, 128.2, 127.5, 124.6, 117.1, Spectral data obtained for the compound are in good agreement with the reported data Phenylquinoline (28). The reaction of 5-nitroquinoline 1A (104 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition [without 18-crown-6 additive] stirred for 24 h, followed by purification by MPLC-Purifespoir 2 (10 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 75:25) gave the title compound (87 mg, 0.43 mmol, 71%) as a light yellow solid. 1 H NMR (400 MHz, CDCl3): δ (m, 1H), 8.24 (d, J = 8.7 Hz, 1H), 8.14 (d, J = 8.7 Hz, 1H), 7.76 (t, J = 8.1 Hz, 1H), (m, 6H), 7.34 (dd, J = 8.7, 4.4 Hz, 1H); 13 C NMR (101 MHz, CDCl3): δ 150.2, 148.5, 140.4, 139.3, 134.3, 130.0, , , 128.4, 127.6, 127.2, 126.6, Spectral data obtained for the compound are in good agreement with the reported data Phenylisoquinoline (29). The reaction of 5-nitroisoquinoline 1B (104 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition [without 18-crown-6 additive] stirred for 14 h, followed by purification by MPLC- Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 65:35) gave the title compound (86 mg, 0.42 mmol, 70%) as a yellow oil. 1 H NMR (400 MHz, CDCl3): δ 9.30 (s, 1H), 8.47 (d, J = 5.4 Hz, 1H), 7.96 (t, J = 4.4 Hz, 1H), 7.72 (d, J = 6.0 Hz, 1H), 7.64 (d, J = 4.0 Hz, 2H), (m, 5H); 13 C NMR (101 MHz, CDCl3): δ 152.8, 143.3, 139.1, 138.9, 134.0, 130.8, 129.7, 128.8, 128.4, 127.7, 127.0, 126.7, Spectral data obtained for the compound are in good agreement with the reported data. 22 N,N-Dimethyl-3'-(methylsulfonyl)-[1,1'-biphenyl]-4-amine (30). The reaction of 1-(methylsulfonyl)-3-nitrobenzene 1n (121 mg, 0.60 mmol) and (4-(dimethylamino)phenyl)boronic acid 2c (148 mg, 0.90 mmol) with optimized condition stirred for 16 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 65:35) gave the title compound (133 mg, 0.48 mmol, 81%) as a white solid [mp ºC (dec.)]. 1 H NMR (400 MHz, CDCl3): δ 8.12 (t, J = 1.6 Hz, 1H), (m, 2H), 7.57 (t, J = 7.6 Hz, 1H), (m, 2H), (m, 2H), 3.08 (s, 3H), 3.02 (s, 6H); 13 C NMR (101 MHz, CDCl3): δ 150.5, 142.7, 140.9, 131.0, 129.7, 127.7, 126.4, 124.6, 124.3, 112.6, 44.5, 40.4; HRMS [APCI(+)] m/z calcd for C15H17NO2S [M+H] + : Found: Methoxy-4'-methyl-1,1'-biphenyl (5). The reaction of 4-nitroanisole 1a (92 mg, 0.60 mmol) and p-tolylboronic acid 2d (122 mg, 0.90 mmol) with optimized condition stirred for 24 h. The crude reaction mixture S10

11 subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (95 mg, 0.48 mmol, 79%) as a white solid. Spectral data obtained for the compound are in good agreement with the reported data. 6 4-(tert-Butyl)-4'-methoxy-1,1'-biphenyl (31). The reaction of 4- nitroanisole 1a (92 mg, 0.60 mmol) and 4-tert-butylphenylboronic acid 2e (160 mg, 0.90 mmol) with optimized condition stirred for 12 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (116 mg, 0.48 mmol, 80%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), (m, 2H), 7.01 (d, J = 8.1 Hz, 2H), 3.88 (s, 3H), 1.41 (s, 9H); 13 C NMR (101 MHz, CDCl3): δ 158.9, 149.6, 137.9, 133.6, 128.0, 126.3, 125.6, 114.1, 55.3, 34.4, Spectral data obtained for the compound are in good agreement with the reported data. 23 1,1':4',1''-Terphenyl (6). The reaction of nitrobenzene 1e (74 mg, 62 L, 0.60 mmol) and [1,1'-biphenyl]-4-ylboronic acid 2f (178 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purifespoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (91 mg, 0.39 mmol, 66%) as a white solid. Spectral data obtained for the compound are in agreement with the data reported. 7 1-(2'-Methoxy-[1,1'-biphenyl]-4-yl)ethan-1-one (32). The reaction of 2- nitroanisole 1p (92 mg, 73 L, 0.60 mmol) and (4-acetylphenyl)boronic acid 2g (197 mg, 1.20 mmol) with optimized condition stirred for 16 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n- hexane/ethyl acetate = 100:0 to 91:9) gave the title compound (77 mg, 0.34 mmol, 57%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 7.4 Hz, 2H), 7.65 (d, J = 8.1 Hz, 2H), (m, 2H), 7.06 (t, J = 7.4 Hz, 1H), 7.02 (d, J = 8.1 Hz, 1H), 3.83 (s, 3H), 2.64 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 197.8, 156.4, 143.5, 135.4, 130.6, 129.7, 129.4, 129.3, 128.0, 120.9, 111.2, 55.5, Spectral data obtained for the compound are in good agreement with the reported data. 24 Methyl 2'-methoxy-[1,1'-biphenyl]-4-carboxylate (33). The reaction of 2-nitroanisole 1p (92 mg, 73 L, 0.60 mmol) and (4- (methoxycarbonyl)phenyl)boronic acid 2h (162 mg, 0.90 mmol) with optimized condition stirred for 16 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (95 mg, 0.39 mmol, 66%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 8.7 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), (m, 2H), 7.06 (t, J = 7.7 Hz, 1H), 7.01 (d, J = 8.1 Hz, 1H), 3.94 (s, 3H), 3.83 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 167.1, 156.4, 143.3, 130.7, 129.5, 129.3, 129.2, 128.4, 120.9, 111.3, 55.5, 52.0 (one 13 C value merged with other peaks). Spectral data obtained for the compound are in good agreement with the reported data. 24 S11

12 2-Methoxy-4'-(trifluoromethyl)-1,1'-biphenyl (34). The reaction of 2- nitroanisole 1p (92 mg, 73 L, 0.60 mmol) and (4- (trifluoromethyl)phenyl)boronic acid 2i (171 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (98 mg, 0.39 mmol, 65%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), 7.42 (t, J = 7.7 Hz, 1H), 7.36 (d, J = 7.4 Hz, 1H), 7.10 (t, J = 7.4 Hz, 1H), 7.06 (d, J = 8.1 Hz, 1H), 3.86 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 156.4, 142.2, 130.7, 129.8, 129.5, 129.1, (q, J = 32.6 Hz) (q, J = 3.8 Hz), (q, J = Hz), 120.9, 111.3, 55.5; 19 F NMR (376 MHz, CDCl3): δ Spectral data obtained for the compound are in good agreement with the reported data. 25 Methyl 4'-(trifluoromethyl)-[1,1'-biphenyl]-3-carboxylate (35). The reaction of methyl 3-nitrobenzoate 1m (109 mg, 0.60 mmol) and (4- (trifluoromethyl)phenyl)boronic acid 2i (171 mg, 0.90 mmol) with optimized condition [base replaced with CsF (0.27 g, 1.8 mmol) and without 18-crown-6 additive] stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (106 mg, 0.38 mmol, 63%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ 8.29 (s, 1H), 8.08 (d, J = 8.1 Hz, 1H), 7.79 (d, J = 7.4 Hz, 1H), (m, 4H), 7.55 (t, J = 8.1 Hz, 1H), 3.96 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 166.8, 143.6, 140.0, 131.6, 130.9, (q, J = 32.6 Hz), 129.2, 129.1, 128.4, 127.5, (q, J = 3.8 Hz), (q, J = Hz), 52.3; 19 F NMR (376 MHz, CDCl3): δ Spectral data obtained for the compound are in good agreement with the reported data Fluoro-4'-methoxy-1,1'-biphenyl (10). The reaction of 4-nitroanisole 1a (92 mg, 0.60 mmol) and 4-fluorophenylboronic acid 2j (126 mg, 0.90 mmol) with optimized condition stirred for 24 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (88 mg, 0.44 mmol, 73%) as a white solid. Spectral data obtained for the compound are in good agreement with the reported data. 6 3-Methoxy-1,1'-biphenyl (11). The reaction of nitrobenzene 1e (74 mg, 62 L, 0.60 mmol) and 3-methoxyphenylboronic acid 2k (137 mg, 0.90 mmol) with optimized condition stirred for 12 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (79 mg, 0.43 mmol, 72%) as a colorless oil. Spectral data obtained for the compound are in good agreement with the reported data Methoxy-2'-methylbiphenyl (36). The reaction of 2-nitroanisole 1p (92 mg, 73 L, 0.60 mmol) and o-tolylboronic acid 2l (122 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (79 mg, 0.40 mmol, 67%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ 7.34 (t, J = 8.1 Hz, 1H), (m, 5H), 7.01 (t, J = 7.4 Hz, 1H), 6.96 (d, J = 8.1 Hz, 1H), 3.76 (s, 3H), 2.14 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 156.6, 138.6, 136.8, 131.0, 130.8, 130.0, 129.6, 128.5, 127.3, S12

13 125.4, 120.4, 110.6, 55.4, Spectral data obtained for the compound are in good agreement with the reported data (2,6-Dimethylphenyl)naphthalene (37). The reaction of 1-nitronaphthalene 1t (104 mg, 0.60 mmol) and (2,6-dimethylphenyl)boronic acid 2m (135 mg, 0.90 mmol) with optimized condition [base replaced with CsF (0.27 g, 1.8 mmol) and without 18-crown-6 additive] stirred for 20 h, followed by purification by MPLC- Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0) gave the title compound (50 mg, 0.22 mmol, 36%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 7.91 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 8.2 Hz, 1H), 7.55 (t, J = 7.8 Hz, 1H), 7.47 (t, J = 6.9 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), 1.91 (s, 6H); 13 C NMR (101 MHz, CDCl3): δ 139.6, 138.7, 137.0, 133.7, 131.7, 128.3, 127.3, , , 126.4, 126.0, , , 125.4, Spectral data obtained for the compound are in good agreement with the reported data (2-Methoxyphenyl)naphthalene (38). The reaction of 2-nitroanisole 1p (92 mg, 73 L, 0.60 mmol) and naphthalen-2-ylboronic acid 2n (155 mg, 0.90 mmol) with optimized condition stirred for 18 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purifespoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 94:6) gave the title compound (113 mg, 0.48 mmol, 81%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.04 (s, 1H), (m, 3H), 7.77 (d, J = 8.1 Hz, 1H), (m, 3H), 7.43 (t, J = 7.7 Hz, 1H), 7.14 (t, J = 7.4 Hz, 1H), 7.08 (d, J = 8.1 Hz, 1H), 3.88 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 156.6, 136.2, 133.4, 132.4, 131.1, 130.6, 128.7, 128.1, 127.5, 127.1, 125.9, 125.7, 120.9, 111.2, 55.5 (two 13 C values merged with other peaks). Spectral data obtained for the compound are in good agreement with the reported data (3-(Methylsulfonyl)phenyl)thiophene (39). The reaction of 1- (methylsulfonyl)-3-nitrobenzene 1n (121 mg, 0.60 mmol) and thiophen-3- ylboronic acid 2o (115 mg, 0.9 mmol) with optimized condition [Pd(acac)2 (10 mol%), base replaced with CsF (0.27 g, 1.8 mmol) and without 18-crown-6 additive] stirred for 16 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 70:30) gave the title compound (58 mg, 0.24 mmol, 41%) as a light yellow color oil. 1 H NMR (400 MHz, CDCl3): δ 8.16 (s, 1H), 7.87 (t, J = 7.1 Hz, 2H), (m, 2H), (m, 2H), 3.09 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 141.1, 140.0, 137.1, 131.3, 129.9, 127.0, 125.9, 125.6, 124.9, 121.9, 44.4; HRMS [APCI(+)] m/z calcd for C11H10O2S2 [M] + : Found: Methoxy-3-(thiophen-3-yl)pyridine (40). The reaction of 2-methoxy-3- nitropyridine 1z (92 mg, 0.60 mmol) and thiophen-3-ylboronic acid 2o (115 mg, 0.90 mmol) with optimized condition stirred for 16 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 92:8) gave the title compound (62 mg, 0.33 mmol, 54%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ 8.12 (dd, J = 5.0, 1.8 Hz, 1H), 7.78 (dd, J = 7.3, 1.8 Hz, 1H), 7.73 (dd, J = 3.0, 1.1 Hz, 1H), 7.47 (dd, J = 5.0, 1.4 Hz, 1H), 7.37 (dd, J = 5.0, 2.7 Hz, 1H), 6.95 (dd, J = 7.3, 5.0 Hz, 1H), 4.04 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 160.5, 145.1, 137.0, 136.4, 127.7, 125.0, 123.8, 119.2, 117.0, 53.5; HRMS [APCI(+)] m/z calcd for C10H9NOS [M+H] + : Found: S13

14 Figure S1. Unsuccessful substrates. S14

15 4. Control experiments Coupling reaction of aniline or nitrosobenzne with 4-methoxyphenylboronic acid A 4-mL Iwaki screw caped vial was charged with aniline or nitrosobenzne (introduced in glove box) (0.10 mmol), 4-methoxyphenylboronic acid (23 mg, 0.15 mmol), Pd(acac)2 (1.5 mg, mmol), BrettPhos (11 mg, mmol), K3PO4 nh2o (80 mg, 0.30 mmol) and 18-crown-6 (2.6 mg, mmol). Subsequently, 1,4-dioxane (0.50 ml) was introduced into the vial in a glove box and the resulting mixture was stirred at 130 C for h. The desired product formation was monitored by GC analysis with tridecane (7.6 mg, mmol) as an internal standard. Coupling reaction in presence of radical scavengers A 4-mL Iwaki screw caped vial was charged with 4-nitroanisole (15.3 mg, 0.10 mmol), phenylboronic acid (18.3 mg, 0.15 mmol), Pd(acac)2 (1.5 mg, mmol), BrettPhos (11 mg, 0.02 mmol), K3PO4 nh2o (80 mg, 0.30 mmol) and 18-crown-6 (2.6 mg, 0.01 mmol). Subsequently, TEMPO (15.6 mg, 0.10 mmol) or galvinoxyl (42.2 mg, 0.10 mmol) was introduced into the vial in a glove box and the resulting mixture was stirred at 130 C for h. The desired product was determined by GC analysis with tridecane (7.6 mg, mmol) as an internal standard. S15

16 5. Stoichiometric reactions Reaction of (cod)pd(ch2sime3)2 with nitrobenzne in the presence of BrettPhos; Synthesis of (BrettPhos)Pd(NO2)Ph (41). A glass tube equipped with a Teflon-valve was charged with (cod)pd(ch2sime3)2 (91.0 mg, mmol), BrettPhos (124.5 mg, mmol) and THF (5.0 ml). Nitrobenzene (1e) (72 L, 0.70 mmol) was added to the above solution, and allowed to stir for 10 min at ambient temperarure. The solution was turned from brown to purple. After the the mixture was heated for 48 h at 60 C, removal of the solvent under reduced pressure gave a black residual solid. The residue was washed five times with 2.0 ml of pentane to remove unreacted BrettPhos and nitrobenzene. The residue was then extracted five times with 2.0 ml of CHCl3, and the combined solution was filtered through celite. Removal of the solvent under reduced pressure gave the title compound as a pale yellow solid (50.1 mg, mmol, 28%). A yellow single crystal suitable for the X-ray diffraction study was prepared by the recrystallization from the mixed solvent of pentane and CHCl3 in a 3:1 volume ratio at ambient temperature. 1 H NMR (400 MHz, CDCl3): 7.20 (d, J = 6.4 Hz, 2H), 7.14 (s, 2H), (m, 5H), 3.82 (s, 3H), 3.37 (s, 3H), 2.82 (sept, J = 6.8 Hz, 1H), 2.66 (m, 2H), 2.52 (sept, J = 6.8 Hz, 2H), 1.83 (d, J = 6.8 Hz, 6H), (m, 10H), 1.23 (d, J = 6.8 Hz, 6H), (m, 7H), (m, 3H), 0.84 (d, J = 6.8 Hz, 6H); 13 C NMR (101 MHz, CDCl3): 154.5, 153.7, 152.0, 151.8, 150.4, 141.6, 138.1, 137.8, 136.4, 126.3, 124.4, 123.6, 116.6, 113.3, 110.9, 55.0, 54.4, 34.8, 34.5, 33.8, 31.6, 29.23, 29.21, 27.8, 27.71, 27.65, 27.58, 26.1, 25.3, 24.6, 22.9 (observed complexity is due to C P coupling); 31 P NMR (162 MHz, CDCl3): 38.3; IR (KBr): 2919, 2850, 1562, 1465 ( asym NO2), 1424, 1366, 1356, 1325, 1256 ( sym NO2), 1250, 1057, 1018, 1007, 735 cm 1 ; HRMS[ESI(+)] calcd for C41H58O4NPPd [M NO2] + : Found: m/z ; Anal. Calcd for C41H58O4NPPd 0.9CHCl3: C, 57.60; H, 6.79; N, Found: C, 57.69; H, 6.95; N, Elemental analysis was carried out using crystals of 4, which were prepared as well as those for X-ray crystallographic analysis. As shown by the X-ray diffraction analysis, the obtained crystals include co-crystallized the equimolar amount of CHCl3 molecule. It was difficult to remove CHCl3 molecule completely even by the long-time evacuation as shown by the results of the elemental analysis, suggesting only 10% of CHCl3 was removed partially. Reaction of (cod)pd(ch2sime3)2 with 1-nitronaphthalene in the presence of BrettPhos; Synthesis of (BrettPhos)Pd(1- nitronaphthalene) (42). A 80-mL Schlenk tube was charged with (cod)pd(ch2sime3)2 (39.4 mg, mmol), BrettPhos (54.8 mg, mmol), 1-nitronaphthalene (1t) (18.0 mg, mmol), and toluene (4.0 ml). The reaction mixture was stirred at ambient temperature for 20 h. Removal of the solvent under reduced pressure gave a purple residual solid. The residue was washed five times with 2.0 ml of hexane to remove unreacted BrettPhos and 1-nitronaphthalene. The residue was then extracted five times with 2.0 ml of toluene, and the combined solution was filtered through a glass filter. Removal of the solvent under reduced pressure gave the title compound as a purple solid (68.4 mg, mmol, 83%). A purple single crystal suitable for the X-ray diffraction study was prepared by the recrystallization from the mixed solvent of pentane and toluene in a 3:1 volume ratio at ambient temperature. 1 H NMR (400 MHz, C6D6): 8.97 (d, J = 8.0 Hz, 1H, C 8 H), 7.80 (d, J = 6.0 Hz, 1H, C 2 H), 7.56 (d, 1H, C 5 H, obscured by the singnal appeared at 7.55), 7.55 (s, 1H), 7.34 (s, 1H), 7.18 (dd, 1H, C 7 H, obscured by the residual proton of the solvent), 7.07 (dd, J = 8.0 Hz, 1H, C 6 H), 6.30 (m, 2H), 6.02 (d, J = 7.2 Hz, 1H, C 4 H), 3.82 (m, 1H, C 3 H), 3.20 (s, 3H), 3.01 (sept, J = 6.8 Hz, 1H), 2.90 (s, 3H), 2.47 (m, 2H), 2.22 (m, 2H), 2.04 (m, 1H), 1.91 (m, 1H), 1.73 (m, 2H), 1.61 (d, J = 6.8 Hz, 3H), (m, 6H), 1.44 (d, J = 6.8 Hz, 6H), 1.37 (d, J = 6.8 Hz, 3H), S16

17 (m, 6H), 1.04 (d, J = 7.2 Hz, 3H), 1.00 (m, 2H), 0.90 (d, J = 6.8 Hz, 3H), 0.84 (m, 1H), 0.17 (m, 1H); COSY (C6D6): H H/ , , , , , , , , , , , , , , , , , ; 13 C NMR (101 MHz, C6D6): 155.3, 152.4, 146.8, 143.8, 142.9, 137.3, , , 130.3, 130.2, 126.6, 126.4, 125.1, 124.6, 123.0, 123.5, 122.0, 120.5, 120.4, 112.2, 110.2, 75.5, 74.2, 74.1, 55.0, 54.1, 39.6, 39.5, 38.5, 38.4, 33.9, 33.7, 33.6, 31.6, 31.4, 31.34, 31.27, 30.39, 30.35, 30.29, 28.1, 28.0, 27.9, 27.8, 27.5, 27.4, 27.1, 26.94, 26.90, 26.1, 25.8, 25.1, 24.7, 24.5, 24.3, 23.9 (observed complexity is due to C P coupling); 31 P NMR (162 MHz, THF-d8): 41.5; IR (KBr): 2958, 2927, 2850, 1577, 1459 ( asym NO2), 1423, 1281, 1252 ( sym NO2), 1197, 1156, 1055, 1016, 762 cm 1 ; Anal. Calcd for C45H60O4NPPd: C, 66.21; H, 7.41; N, Found: C, 66.05; H, 7.71; N, Reaction of (BrettPhos)Pd(NO2)(Ph) (41) with 4-methoxyphenylboronic acid (2b) in the presence of K3PO4 nh2o. An NMR tube equipped with a Teflon valve was charged with 41 (19.8 mg, mmol), 2b (7.8 mg, mmol), and K3PO4 nh2o (27.5 mg, mmol). Subsequently, THF-d8 (0.75 ml) and tridecane (5.0 L) as an internal standard were introduced into the tube under N2 atmosphere. The reaction proceeded at 25 ºC, and the GC spectra recorded after 24 h showed the formation of 3 in 51% yield. Reaction of (BrettPhos)Pd(NO2)(Ph) (41) with 4-methoxyphenylboronic acid (2b) in the absence of a base. An NMR tube equipped with a Teflon valve was charged with 41 (19.8 mg, mmol) and 2b (7.8 mg, mmol). Subsequently, THF-d8 (0.75 ml) and tridecane (5.0 L) as an internal standard were introduced into the tube under N2 atmosphere. The resulting mixture was heated at 60 C for 24 h, and the GC analysis showed the formation of 3 in 39% yield. Reaction of (BrettPhos)Pd(NO2)(Ph) (41) with 4-bromo-n-butylbenzene. An NMR tube equipped with a Teflon valve was charged with 41 (19.4 mg, mmol), 4-bromo-n-butylbenzene (3.8 µl, mmol), and THF-d8 (0.75 ml) under N2 atmosphere. The resulting mixture was heated at 50 C for 4 h, and the NMR analysis showed the formation of (BrettPhos)Pd(Br)(p-n-BuC6H4) P NMR spectra of the reaction mixute are listed in Figure S2. S17

18 Figure S2. 31 P NMR profiles before and after the reaction. S18

19 6. Sequential Functionalization of Nitroarenes Scheme S1. Sequential Functionalizations of Nitroarenes 9-([1,1'-Biphenyl]-4-yl)-9H-carbazole (55). The reaction of 9-(4- nitrophenyl)-9h-carbazole 54 (173 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 16 h. The crude reaction mixture subjected to oxidation condition (CH2Cl2 solvent) followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 92:8) gave the title compound (112 mg, 0.35 mmol, 59%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ 8.17 (d, J = 7.8 Hz, 2H), 7.83 (d, J = 8.7 Hz, 2H), 7.70 (d, J = 7.3 Hz, 2H), 7.65 (d, J = 8.2 Hz, 2H), (m, 7H), 7.31 (t, J = 7.8 Hz, 2H); 13 C NMR (101 MHz, CDCl3): δ 140.8, 140.3, 136.8, 128.9, 128.5, 127.6, 127.3, 127.1, 126.0, 123.4, 120.3, 120.0, (one 13 C value merged with other peaks). Spectral data obtained for the compound are in agreement with the reported data. 33 S19

20 4-Phenoxy-1,1'-biphenyl (57). The reaction of 1-nitro-4-phenoxybenzene 56 (129 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purifespoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (99 mg, 0.40 mmol, 67%) as a white solid. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), 7.44 (t, J = 7.4 Hz, 2H), (m, 3H), 7.14 (t, J = 7.4 Hz, 1H), (m, 4H); 13 C NMR (101 MHz, CDCl3): δ 157.1, 156.8, 140.5, 136.2, 129.8, 128.8, 128.4, 127.0, 126.9, 123.4, (one 13 C value merged with other peaks). Spectral data obtained for the compound are in agreement with the reported data Phenoxy-1,1'-biphenyl (59). The reaction of 1-nitro-2-phenoxybenzene 58 (129 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition stirred for 16 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 96:4) gave the title compound (92 mg, 0.37 mmol, 62%) as a viscous liquid. 1 H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 7.4 Hz, 2H), 7.45 (d, J = 7.4 Hz, 1H), 7.35 (t, J = 7.7 Hz, 2H), (m, 5H), 7.01 (t, J = 8.4 Hz, 2H), 6.92 (d, J = 8.1 Hz, 2H); 13 C NMR (101 MHz, CDCl3): δ 157.8, 153.6, 137.7, 133.7, 131.3, 129.6, 129.2, 128.7, 128.1, 127.2, 124.0, 122.6, 120.1, Spectral data obtained for the compound are in agreement with the reported data. 35 Ethyl 2-([1,1'-biphenyl]-4-yl)propanoate (61). The reaction of ethyl 2- (4-nitrophenyl)propanoate 60 (134 mg, 0.60 mmol) and phenylboronic acid 2a (110 mg, 0.90 mmol) with optimized condition [base replaced with CsF (0.27 g, 1.8 mmol) and without 18-crown-6 additive] stirred for 14 h. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC- Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 95:5) gave the title compound (108 mg, 0.42 mmol, 71%) as a colorless oil. 1 H NMR (400 MHz, CDCl3): δ (m, 4H), (m, 4H), 7.38 (t, J = 7.3 Hz, 1H), (m, 2H), 3.81 (q, J = 7.3 Hz, 1H), 1.59 (d, J = 7.3 Hz, 3H), 1.27 (t, J = 7.3 Hz, 3H); 13 C NMR (101 MHz, CDCl3): δ 174.4, 140.7, 139.9, 139.6, 128.7, 127.8, , , 127.0, 60.7, 45.1, 18.5, Spectral data obtained for the compound are in agreement with the reported data. 36 Methyl 2'-nitro-[1,1'-biphenyl]-4-carboxylate (62). The reaction of nitrobenzene 1e (0.74 g, 0.61 ml, 6.0 mmol) and methyl 4- bromobenzoate (129 mg, 0.60 mmol) with Fagnou condition [Pd(OAc)2 (5.0 mol%), P t Bu2MeHBF4 (15 mol%), PivOH (0.30 equiv) and K2CO3 (1.3 equiv) in mesitylene solvent] 32 stirred at 125 o C for 16 h, followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 90:10) gave the title compound (82 mg, 0.32 mmol, 53%) as a white solid [mp ºC (dec.)]. 1 H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 8.2 Hz, 2H), 7.91 (d, J = 8.2 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.52 (t, J = 7.8 Hz, 1H), 7.43 (d, J = 7.3 Hz, 1H), 7.38 (d, J = 8.2 Hz, 2H), 3.93 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 166.5, 148.8, 142.1, 135.4, 132.6, 131.7, , , 128.8, 127.9, 124.3, 52.2; HRMS [APCI(+)] m/z calcd for C14H11NO4 [M+H] + : Found: S20

21 Methyl [1,1':2',1''-terphenyl]-4-carboxylate (63). The reaction of methyl 2'-nitro-[1,1'-biphenyl]-4-carboxylate 6e (154 mg, 0.60 mmol) and phenylboronic acid 62 (183 mg, 1.50 mmol) with optimized condition stirred at 150 ºC for 30 h [RuPhos (56 mg, 0.12 mmol) was used instead of BrettPhos]. The crude reaction mixture subjected to oxidation condition followed by purification by MPLC-Purif-espoir 2 (25 g Biotage SNAP Ultra column (25 m size), n-hexane/ethyl acetate = 100:0 to 97:3) gave the title compound (90 mg, 0.31 mmol, 52%) as a white solid [mp ºC (dec.)]. 1 H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 8.2 Hz, 2H), (m, 4H), (m, 5H), (m, 2H), 3.89 (s, 3H); 13 C NMR (101 MHz, CDCl3): δ 167.1, 146.4, 141.0, 140.6, 139.5, 130.7, 130.4, 129.9, 129.8, 129.2, 128.1, 128.0, 127.6, 126.7, 52.0 (one 13 C value merged with other peaks); HRMS [APCI(+)] m/z calcd for C20H16O2 [M+H] + : Found: S21

22 7. Competitive Reaction A 4-mL Iwaki screw caped vial was charged with 4-nitroaisole 1a (46 mg, 0.30 mmol), 1-nitro-4- (trifluoromethyl)benzene 1h (57 mg, 0.30 mmol), phenylboronic acid 2a (37 mg, 0.30 mmol), Pd(acac)2 (4.6 mg, mmol), and BrettPhos (32 mg, mmol). Subsequently, CsF (0.14 g, 0.90 mmol) and 1,4-dioxane (1.5 ml) were introduced into the vial in a glove box under N2 atmosphere and the vial was taken outside. The reaction mixture was stirred at 130 ºC for 24 h. After completion of the reaction, it was allowed to cool to room temperature. The reaction mixture was passed through a short pad of celite with ethyl acetate and concentrated under reduced pressure. The yields of 3 and 67 were determined by NMR analysis using 1,3,5-trimethoxybenzene and hexafluorobenzene as internal standards. Density functional theory (DFT) calculation for the oxidative addition step Figure S3. Energy diagram of the oxidative addition of 4-nitroanisole 1a and 1-nitro-4- (trifluoromethyl)benzene 1h (Computational details are given in section 10). S22

23 8. X-ray diffraction studies Data of 41 and 42 were collected on a Rigaku/Saturn70 CCD diffractometer using graphitemonochromated MoKα radiation (λ = Å) at 143 K, and processed using CrystalClear (Rigaku). 37,38 The structures were solved by a direct method using SHELXT-2014/5 program and refinement was carried out by least-squares methods based on F 2 with all measured reflections usig SHELXL-2014/7 program. 39,40 The non-hydrogen atoms were refined anisotropically. (a) (b) P1 Pd1 C1 N1 O2 P1 Pd1 C4 C3 O2 N1 C15 O1 C19 O1 Figure S4. (a) Single-crystal X-ray diffraction structure of 41 (atomic displacement paramters set at 30% probability; hydrogen atoms and CHCl3 solvate molecules omitted for clarity; only selected atoms are labeled). Selected bond lengths (Å): Pd1 N (3), Pd1 C (4), Pd1 P (10), and Pd1 C (3). Selected bond angles (º): N1 Pd1 C (13), C1 Pd1 P (10), P1 Pd1 C (8), and C15 Pd1 N (12); (b) Single-crystal X-ray diffraction structure of 42 (atomic displacement paramters set at 30% probability; hydrogen atoms omitted for clarity; only selected atoms are labeled). Selected bond lengths (Å): Pd1 C (2), Pd1 C (2), Pd1 P (5), Pd1 C (18), and C3 C (3). Selected bond angles (º): C3 Pd1 C (8), C4 Pd1 P (6), P1 Pd1 C (5), and C19 Pd1 C (7). S23

24 Table S2. Crystallographic data for 41 and (a) Crystal Data Empirical Formula C 41H 58NO 4PPd CHCl 3 C 45H 60NO 4PPd Formula Weight Crystal Description Prism Prism Crystal Color Yellow Purple Crystal size (mm) Crystallizing Solution CHCl 3/pentane toluene/hexane Crystal System Triclinic Orthorhombic Space Group P-1 (#2) Pbca (#61) Lattice Parameters a = (2) Å a = (8) Å b = (2) Å b = (9) Å c = (4) Å c = (9) Å = (10) º = 90 º = (2) º = 90 º = (2) º = 90 º V (Å 3 ) (8) (6) Z value 2 8 D calc (g/cm 3 ) Measuremant Temp 130 ºC 130 ºC (MoK ) (mm -1 ) (b) Intensity Measurements Diffractometer Rigaku Saturn70 Rigaku Saturn70 radiation MoK MoK Monochromator Graphite Graphite Reflections Collected Independent reflections 9643 (R int = ) 9213 (R int = ) Reflections Observed (>2 ) Abs. Correction type Empirical Empirical Abs. Transmission (min.) (min.) (max.) (max.) (c) Refinement (Shelxl-2014/7) R 1 (I<2 ) wr 2 (I<2 ) R 1 (all data) wr 2 (all data) Data/Restraints/Parameters 9643 / 0 / / 0 / 529 GOF Largest diff. peak and hole and e.å and e.å -3 S24

25 9. Ion chromatography The crude reaction mixture of cross-coupling reaction between 1p (0.60 mmol) and 2a (0.90 mmol) under the optimized conditions (Pd(acac)2 (9.1 mg, mmol), BrettPhos (64 mg, mmol), K3PO4 nh2o (0.48 g, 1.80 mmol) and 18-crown-6 (16 mg, mmol) in 1,4-dioxane (3.0 ml) stirred at 130 o C for 20 h) was extracted with distilled water. Inorganic anions in the aqueous solution were analyzed by ion chromatography. The similar experiment was also carried out with CsF (0.27 g, 1.80 mmol) base. Figure S5. Ion chromatograph of the aqueous solution obtained from the cross-coupling reaction using K3PO4 nh2o as a base. [min] Table S3. Results of the ion chromatograph shown in Figure S5. Retention Area Concentration time (min) (us sec) (mg/l) NO NO [min] Figure S6. Ion chromatograph of the aqueous solution obtained from the cross-coupling reaction using CsF as a base. Table S4. Results of the ion chromatograph shown in Figure S6. Retention Area Concentration time (min) (us sec) (mg/l) NO NO S25

26 10. Computational details All geometry optimizations were performed by the density functional theory (DFT) with the ωb97xd functional 41 because this functional reproduced the geometry of the product in oxidative addition of nitrobenzene to Pd(0)(BrettPhos). The Stuttgart-Dresden-Bonn (SDB) basis sets were used for Pd and Cs atoms with the effective core potentials (ECPs). 42,43 The 6-31G(d) basis sets were used for all other atoms. Single-point calculations were performed to evaluate better potential energies, using better basis sets; for Pd, 2f polarization functions were added, 44 and for Cs, one d polarization function was added. 45 Usual 6-311G(d) basis sets were used for other atoms, 46,47 where a set of diffuse functions was added to anionic F, O, and N of OH and NO2. 48 In the single-point calculations, the B3PW91-D3 functional was employed because the B3PW91-D3-calculated energy changes agreed with the MP4(SDQ) and SCS-MP2-calculated energy changes of several model reactions; we checked various functionals such as M06, M06L, M06HX, M06-2X, ωb97xd, B3LYP-D3, and B3PW91-D3. Solvation effects of dioxane were evaluated with the PCM method The Gibbs energy was employed for discussion, where the translation entropy in solution was corrected by the method of Whiteside et al. 58 All these calculations were carried out with Gaussian09 program. 59 Possibility of Transmetallation between Pd(Ph)(F)(Brettphos) and PhB(OH)2 Because it was experimentally reported that ArB(OH)3-n(F)n (n = 0-3) species can be formed spontaneously but they react much more slowly than do [Pd] X (X = OH, F) with ArB(OH)2, 60, 61 we investigated CsF participates in the transmetallation between Pd(II)(NO2)(C6H4OMe-p)(BrettPhos) 46 and PhB(OH)2 2. The calculations show that CsF reacts with the Pd center to afford Pd(II)(F)(Ph)(Prettphos) 67 (Figure S7) in which NO2 ligand is substituted for by the F ligand. Then, PhB(OH)2 approaches the F ligand to form 68. Transmetallation occurs through a transition state TS68-50 to afford Pd(II)(Ph)(C6H4OMe-p)(Brettphos) 50. The Gibbs activation energy ( Gº ) is calculated to be 24.2 kcal/mol. This value is smaller than that calculated for the transmetallation between 46 and Cs[Ph B(OH)2F] adduct 47, as reported previously. 60,61 However, the formation of 47 is much exergonic, as shown in Figure S7. As a result, the transition state TS48-50 of transmetallation between 46 and 47 is calculated to be lower in energy than TS These computational results indicate that the transmetallation via TS48-50 is preferred to that via TS Based on these results, it is likely concluded that (i) when CsF exists in excess to PhB(OH)2 the transmetallation between 46 and Cs[Ph B(OH)2F]adduct 47 is preffered to that between Pd(II)(F)(Ph)(Prettphos) 67 and PhB(OH) 2 but (ii) when CsF concentration is not enough the transmetallation between 67 and 2 is preferred to that between 46 and 47. S26

27 Figure S7. Two plausible pathways for transmetallation step. a a In energetics here, the formation energy of the adduct 47 between phenylboronic acid and CsF is taken into consideration to make comparison with the transmetallation between 67 and 2 in which the formation of the B F interaction is involved. Thus, the energy change going from 46 to 48 is different from that in Figure 1. The details of transmetallation of Figure 1. In Figure 1, the formation of Cs[Ph B(OH)2F] adduct 47 is not involved unlike in Figure S7. This is reasonable because the adduct formation occurs easily due to the large exergonicity, independent on the catalytic cycle: CsF + PhB(OH)2 Cs[Ph B(OH)2F] 47 (S1) where the Gº is 21.4 kcal/mol. In Figure 1, the interaction of Cs{FB(OH)2} with the palladium(ii) complex is shown during the transmetallation, because of the following reasons: (i) 48 is an intermediate before the transmetallation. In 48, NO2 already dissociates from the Pd center but interacts with the Cs. The CsF moiety interacts with the phenylboronic acid. Therefore, CsF must be involved in 48. (ii) In transition state TS48-50, the B C(Ph) distance is elongated to Å and the B F distance becomes shorter (1.397 Å), indicating that the B F bond becomes stronger but the B C distance is not very long. This B-C distance suggests that some bonding interaction still remains between the B and the Ph group. The Pd F distance is Å, indicating that the coordinate bond is very weak but the electrostatic attractive interaction still exists between the Pd(II) and the F anion. The Cs O(B) distance is Å and the Cs F distance is Å, suggesting that some attractive interaction such as electrostatic one exists between the Cs and the OH group and between the Cs and the F atom. (iii) Actually, TS48-50 becomes 13.7 kcal/mol (the Gibbs energy) more unstable by removing the Cs(NO2) group. On the basis of these results, it is likely concluded that the Cs(NO2) group must be involved in TS IRC calculation shows that TS48-50 connects 48 and Pd(Ph)(C6H4OMe-p)(Brettphos) Cs(NO2){FB(OH)2} in which Cs(NO2){FB(OH)2} 49 is distant from Pd(Ph)(C6H4OMep)(Brettphos) 50 and does not seem to interact with 50. These results suggest that Cs(NO2){FB(OH)2} is going to dissociate from the Pd in TS48-50 and completely dissociates from the Pd of 50 in the final stage. S27

28 Coordinates of calculated structure for 4-nitroanisole (1a) C C C C C C H H H H N O O O C H H H Coordinates of calculated structure for Pd(BrettPhos) (43) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H S28

29 H H H H H H H H H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H Coordinates of calculated structure for the most stable isomer of adduct in the oxidative addition (44) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H S29

30 C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H C C C C C C H H H H N O O O C H H H Coordinates of calculated structure for the adduct in the oxidative addition (45) C C C C C C C C S30

31 C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H C C C C C C H H H H N O O O C H S31

32 H H Coordinates of calculated structure for the transition state of the oxidative addition (TS45-46) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C H H H H S32

33 H H H C C C H H H H H H H O C H H H C C C C C C H H H H N O O O C H H H Coordinates of calculated structure for the oxidative addition complex (46) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H S33

34 C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H N O O C C C H H H H H H H C C C H H H H H H H O C H H H O C H H H Coordinates of calculated structure for the complex of phenylboronic acid and CsF (47) Cs F C C C C C C H H H H S34

35 H B O H O H Coordinates of calculated structure for the adduct of transmetalation (48) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C S35

36 C H C H C H H C C C H H H H H H H C C C H H H H H H H O C H H H O C H H H C C C C C C H H H H H B O H O H F Cs O O N Coordinates of calculated structure for the transition state of transmetallation (TS48-50) C C C C C C C C C C C C H H H H O C S36

37 H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H C C C H H H H H H H C C C H H H H H H H O C H H H O C H H H C C C C C C H H H H H S37

38 B O H O H F Cs O O N Coordinates of calculated structure for the complex of borofluoridic acid and CsNO2 (49) B O H O H F Cs O O N Coordinates of calculated structure for the bis(aryl)complex (50) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H S38

39 C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H C C C H H H H H H H C C C H H H H H H H O C H H H O C H H H C C C C H C H C H H H Coordinates of calculated structure for the transition state of reductive elimination (TS50-51) S39

40 C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H C C C H H H H H H H C C C H H H H H H H O C H H H C C C C H C H C H S40

41 H O C H H H C C C C H C H C H H H Pd Coordinates of calculated structure for the biaryl complex (51) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H S41

42 H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H C C C C C C H H H H O C H H H C C C C H C H C H H H Coordinates of calculated structure for the most stable isomer in the reductive elimination (52) C C C C C C C C C C C C H H H H S42

43 O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H C C C C C C H H H H O C H H H C C C C H C H C H S43

44 H H Coordinates of calculated structure for 4-methoxy-1,1'-biphenyl (3) C C C C C C H H H H O C H H H C C C C H C H C H H H Coordinates of model for functional test calculation Model fragment 1 Pd C C C C H C H C H H O C H H H C C C C C C H H H H H S44

45 Model fragment 2 B O H O H F Cs O O N Model AD1 Pd C C C C H C H C H H O C H H H C C C C C C H H H H H B O H O H F Cs O O N S45

46 Coordinates of calculated structure for 1-nitro-4-(trifluoromethyl)benzene (1h) C C C C C C H H H H N O O C F F F Coordinates of calculated structure for the most stable isomer of adduct in the oxidative addition (64) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H S46

47 H H C H H H H H H H H H H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H C C C C C C H H H H N O O C F F F Coordinates of calculated structure for the adduct in the oxidative addition (65) C C C C C C C C C C C C H H H H O C S47

48 H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C H H H H H H H C C C H H H H H H H O C H H H C C C C C C H H H H N O O C F F F S48

49 Coordinates of calculated structure for the transition state of the oxidative addition (TS65-66) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C H H H H H H H C S49

50 C C H H H H H H H O C H H H C C C C C C H H H H N O O C F F F Coordinates of calculated structure for the oxidative addition complex (66) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H S50

51 H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H N O O C C C H H H H H H H C C C H H H H H H H O C H H H C F F F Coordinates of calculated structure for CsF F Cs Coordinates of calculated structure for CsNO2 Cs O N O Coordinates of calculated structure for the (aryl)(fluoride)complex (67) S51

52 C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H C C C H H H H H H H C C C H H H H H H H O S52

53 C H H H O C H H H F Coordinates of calculated structure for phenylboronic acid (2a) C C C C C C H H H H H B O H O H Coordinates of calculated structure for the adduct of transmetalation (68) C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H S53

54 C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H C C C H H H H H H H C C C H H H H H H H O C H H H O C H H H F C C C C C C H H H H H B O H O H Coordinates of calculated structure for the transition state of transmetallation (TS68-50) S54

55 C C C C C C C C C C C C H H H H O C H H H P C C C C H C H C H H H C C C C H C H C H H H C H C H H H C H H H H H H H H H H H H H H H Pd C C C C H C H C H H C C C H H H H H H H C C C H H H H H H H O S55

56 C H H H O C H H H F C C C C C C H H H H H B O H O H Coordinates of calculated structure for borofluoridic acid B O H O H F S56

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