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1 Decarboxylative Biaryl Synthesis from Aromatic Carboxylates and Aryl Triflates Lukas J. Gooßen*, Nuria Rodríguez, Christophe Linder B Chemie rganische Chemie, TU Kaiserslautern, Erwin-Schrödinger-Strasse, Geb. 54, Kaiserslautern, Germany Supporting Information General Procedures Spectroscopic data S2-S13 S14-S61 S1

2 Experimental procedures and data General Methods. Reactions were performed in oven-dried glassware under a nitrogen atmosphere containing a teflon-coated stirrer bar and dry septum. All microwave irradiation experiments were carried out in oven-dried appropriate microwave process tubes (10 ml) under an argon atmosphere containing a teflon-coated stirrer bar and dry septum. or the exclusion of atmospheric oxygen from the reaction media, three freeze-pump thaw cycles were preformed before the reagents were mixed. Solvents were purified by standard procedures prior to use. All reactions were monitored by GC using n-tetradecane as an internal standard. Response factors of the products with regard to n-tetradecane were obtained experimentally by analyzing known quantities of the substances. GC analyses were carried out using an HP-5 capillary column (Phenyl Methyl Siloxane 30 m x 320 x 0.25, 100/ /3) and a time program beginning with 2 min at 60 o C followed by 30 o C/min ramp to 300 C, then 3 min at this temp. Column chromatography was performed using a Combi lash Companion-Chromatography-System (Isco-Systems) and RediSep packed columns (12 g). NMR spectra were obtained on Bruker AMX 400 or on Bruker Avance 600 systems using CDCl 3, methanol-d 4 and D 2 as solvents, with proton and carbon resonances at 400/600 MHz and 101/151 MHz, respectively. Mass spectral data were acquired on a GC-MS Saturn 2100 T (Varian). Microwave assisted reactions were performed using the Discover LabMate with CEM's ChemDriver TM reaction monitoring software. 1-Methyl-2-pyrrolidone (NMP) was dried by removing water as a toluene azeotrope. Copper salts and palladium(ii) iodide were dried in vacuo at 60 C and 80 C respectively, prior to use. All potassium salts were dried for 2 hours in vacuo at room temperature prior to use. All other compounds are commercially available and were used without further purification. S2

3 General procedure for the synthesis and characterization of potassium salts of the carboxylic acids. A 250 ml, two-necked, round-bottomed flask was charged with the carboxylic acid (20.0 mmol) and ethanol (20.0 ml). To this, a solution of potassium tert-butoxide (2.24 g, 20.0 mmol) in ethanol (20.0 ml) was added dropwise over 2 h. After complete addition, the reaction mixture was stirred for another 1 h at room temperature. A gradual formation of a white precipitate was observed. The resulting solid was collected by filtration through a 7-cm Büchner funnel, washed sequentially with ethanol (2 x 10.0 ml) and cold (0 C) diethyl ether (10.0 ml), transferred to a round-bottomed flask, and dried at 2 x 10-3 mmhg to provide the corresponding potassium salts of the carboxylic acids in % yield. Potassium 3-nitrobenzoate (1a). Compound 1a was prepared from 3-nitrobenzoic acid (3.34 g, 20.0 mmol) yielding 1a as a white powder (3.77 g, 92 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 3-nitrobenzoate [CAS: ]. Potassium 4-nitrobenzoate (1b). Compound 1b was prepared from 4-nitrobenzoic acid (3.34 g, 20.0 mmol) yielding 1b as a white powder (3.92 g, 95 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 4-nitrobenzoate [CAS: ]. Potassium 3-cyanobenzoate (1c). Compound 1c was prepared from 3-cyanobenzoic acid (2.94 g, 20.0 mmol) yielding 1c as a white powder (3.47 g, 94 %). 1 H NMR (600 MHz, methanol-d 4 ): δ = 8.24 (t, J = 1.4 Hz, 1H), 8.21 (ddd, J = 7.8, 1.4, 1.3 Hz, 1H), 7.74 (dt, J = 7.7, 1.4 Hz, 1H), 7.54 (t, J = 7.7 Hz, 1H) ppm; 13 C NMR (151 MHz, methanol-d 4 ): δ = 172.4, 140.7, 134.7, 134.5, 133.9, 130.0, 119.8, ppm. Anal. Calcd for C 8 H 4 KN 2 : C, 51.9; H, 2.2; N, 7.6. ound: C, 51.8; H, 2.1; N, 7.6. Potassium 4-cyanobenzoate (1d). Compound 1d was prepared from 4-cyanobenzoic acid (2.94 g, 20.0 mmol) yielding 1d as a white powder (3.58 g, 97 %). The analytical data (NMR, S3

4 CHN analysis) matched those reported in the literature for potassium 4-cyanobenzoate [CAS: ]. Potassium 3-methyl-4-nitrobenzoate (1e). Compound 1e was prepared from 3-methyl- 4-nitrobenzoic acid (3.62 g, 20.0 mmol) yielding 1e as a white powder (4.17 g, 95 %). 1 H NMR (600 MHz, methanol-d 4 ): δ = 7.93 (d, J = 0.5 Hz, 1H), (m, 1H), (m, 1H), 2.56 (s, 3H) ppm; 13 C NMR (151 MHz, methanol-d 4 ): δ = 172.9, 151.4, 143.6, 134.4, 133.7, 128.6, 125.0, 20.2 ppm. Anal. Calcd for C 8 H 6 KN 4 : C, 43.8; H, 2.7; N, 6.4. ound: C, 43.8; H, 2.6; N, 6.3. Potassium 3-chlorobenzoate (1f). Compound 1f was prepared from 3-chlorobenzoic acid (3.13 g, 20.0 mmol) yielding 1f as a white powder (3.61 g, 93 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 3-chlorobenzoate [CAS: ]. Potassium 4-acetamidobenzoate (1g). Compound 1g was prepared from 4-acetamidobenzoic acid (3.58 g, 20.0 mmol) yielding 1g as a white powder (4.21 g, 97 %). 1 H NMR (600 MHz, methanol-d 4 ): δ = 7.90 (d, J = 8.7 Hz, 2H), 7.55 (d, J = 8.4 Hz, 2H), 2.12 (s, 3H) ppm; 13 C NMR (151 MHz, methanol-d 4 ): δ = 174.8, 171.7, 141.9, 134.2, 131.1, 119.8, 23.9 ppm. Anal. Calcd for C 9 H 8 KN 3 : C, 49.7; H, 3.7; N, 6.4. ound: C, 48.0; H, 4.0; N, 6.2. Potassium nicotinate (1h). Compound 1h was prepared from nicotinic acid (2.46 g, 20.0 mmol) yielding 1h as a white powder (3.15 g, 98 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium nicotinate [CAS: ]. Potassium thiophene-3-carboxylate (1i). Compound 1i was prepared from thiophene- 3-carboxylic acid (2.56 g, 20.0 mmol), yielding 1i as a white powder (3.02 g, 91 %). 1 H NMR (600 MHz, methanol-d 4 ): δ = 7.87 (dd, J=3.1, 1.3 Hz, 1 H) 7.44 (dd, J = 5.0, 1.2 Hz, 1H), 7.28 (dd, J = 5.1, 3.1 Hz, 1H) ppm; 13 C NMR (151 MHz, methanol-d 4 ): δ = 171.6, 143.1, 130.0, 129.8, ppm. Anal. Calcd for C 5 H 3 K 2 S: C, 36.1; H, ound: C, 36.1; H, 1.7. S4

5 Potassium 2-fluorobenzoate (1j). Compound 1j was prepared from 2-fluorobenzoic acid (2.80 g, 20.0 mmol) yielding 1j as a white powder (3.39 g, 95 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 2-fluorobenzoate [CAS: ]. Potassium 2-acetylbenzoate (1k). Compound 1k was prepared from 2-acetylbenzoic acid (3.28 g, 20.0 mmol) yielding 1k as a white powder (3.27 g, 81 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 2-acetylbenzoate [CAS: ]. Potassium 2-metoxybenzoate (1l). Compound 1l was prepared from 2-metoxybenzoic acid (3.04 g, 20.0 mmol) yielding 1l as a white powder (3.72 g, 98 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 2-metoxybenzoate [CAS: ]. Potassium thiophene-2-carboxylate (1m). Compound 1m was prepared from thiophene- 2-carboxylic acid (2.56 g, 20.0 mmol) yielding 1m as a white powder (3.13 g, 94 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium thiophene-2-carboxylate [CAS: ]. Potassium furan-2-carboxylate (1n). Compound 1n was prepared from furan-2-carboxylic acid (2.24 g, 20.0 mmol) yielding 1n as a white powder (2.82 g, 94 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium furan- 2-carboxylate [CAS: ]. Potassium 2-nitrobenzoate (1o). Compound 1o was prepared from 2-nitrobenzoic acid (3.34 g, 20.0 mmol) yielding 1o as a white powder (4.01 g, 98 %). The analytical data (NMR, CHN analysis) matched those reported in the literature for potassium 2-nitrobenzoate [CAS: ]. S5

6 General procedure for the synthesis and characterization of aryl triflates. A solution of trifluoromethanesulfonic anhydride (4.00 ml, 24.0 mmol) in CH 2 Cl 2 (10.0 ml) was added dropwise to a solution of pyridine (3.23 ml, 40.0 mmol) and the corresponding phenol (20.0 mmol) in anhydrous CH 2 Cl 2 (20 ml) at 0 C. After complete addition, the mixture was warmed to room temperature and allowed to stir for 1 hour. The mixture was then diluted with Et 2, quenched with 10 % aq HCl and washed successively with sat. NaHC 3, and brine. After drying (MgS 4 ), the solvent was removed under reduced pressure and the residue was purified by Kugelrohr distillation to give the triflates 2 in 91 99% yield. 4-Methylphenyl trifluoromethanesulfonate (2a). Compound 2a was prepared from 4-methylphenol (2.09 ml, 20.0 mmol) yielding 2a as colorless oil (4.70 g, 97 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-methylphenyl trifluoromethanesulfonate [CAS: ]. 2-Naphthyl trifluoromethanesulfonate (2b). Compound 2b was prepared from 2-naphtol (2.88 ml, 20.0 mmol), yielding 2b as a white solid (4.52 g, 82 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-naphthyl trifluoromethanesulfonate [CAS: ]. 3-Acethylphenyl trifluoromethanesulfonate (2c). Compound 2c was prepared from 3- acethylphenol (2.72 g, 20.0 mmol), yielding 2c as a colorless oil (5.14 g, 96 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3- acethylphenyl trifluoromethanesulfonate [CAS: ]. Phenyl trifluoromethanesulfonate (2d). Compound 2d was prepared from phenol (1.76 ml, 20.0 mmol) yielding 2d as colorless oil (3.90 g, 86 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for phenyl trifluoromethanesulfonate [CAS: ]. 4-Methoxyphenyl trifluoromethanesulfonate (2e). Compound 2e was prepared from 4-methoxyphenol (2.48 g, 20.0 mmol) yielding 2e as colorless oil (4.80 g, 94 %). The S6

7 spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-methoxyphenyl trifluoromethanesulfonate [CAS: ]. 2-Methylphenyl trifluoromethanesulfonate (2f). Compound 2f was prepared from 2-methylphenol (2.07 ml, 20.0 mmol) yielding 2f as colorless oil (4.00 g, 83 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-methylphenyl trifluoromethanesulfonate [CAS: ]. 4-Propionylphenyl trifluoromethanesulfonate (2g). Compound 2g was prepared from 1-(4-hydroxyphenyl)propan-1-one (2.91 ml, 20.0 mmol) yielding 2g as colorless oil (4.99 g, 88 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-propionylphenyl trifluoromethanesulfonate [CAS: ]. 4-Chlorophenyl trifluoromethanesulfonate (2h). Compound 2h was prepared from 4-chlorophenol (2.57 g, 20.0 mmol), yielding 2h as colorless oil (4.99 g, 96 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-chlorophenyl trifluoromethanesulfonate [CAS: ]. 2-Quinolyl trifluoromethanesulfonate (2i). Compound 2i was prepared from quinolin-8-ol (2.90 ml, 20.0 mmol), yielding 2i as a white solid (5.23 g, 97 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-quinolyl trifluoromethanesulfonate [CAS: ]. General procedure for the biaryl synthesis (Method A, Table 2). An oven-dried 20 ml vessel was charged with potassium salt of the carboxylic acid (1a-l) (0 mmol), copper(i) oxide (10.7 mg, mmol), palladium(ii) iodide (10.8 mg, 0.03 mmol), 1,10-phenanthroline (27.0 mg, 0.15 mmol) and Tol-BINAP (30.5 mg, mmol). The reaction vessel was evacuated and flushed with nitrogen three times. Subsequently, a solution of 4-methylphenyl trifluoromethanesulfonate (2a) (480 mg, 2.00 mmol) and the internal standard n-tetradecane (50 µl) in NMP (4 ml) was added via syringe. The resulting mixture S7

8 was stirred at 170 C for 24 h, diluted with aqueous HCl (1N, 10 ml) and extracted with ethyl acetate (3 x 20.0 ml). The combined organic layers were washed with water and brine, dried over MgS 4, filtered, and the volatiles were removed in vacuo. The residue was purified by column chromatography (Si 2, ethyl acetate/hexane gradient), yielding the corresponding biaryl. Method B (Table 2). Method B is analogous to Method A but with a lower loading of a modified catalyst. The following amounts were used: potassium salt of the carboxylic acid (1m-o) (0 mmol), copper(i) oxide (7.2 mg, 0.05 mmol), palladium(i) iodide (7.2 mg, 0.02 mmol), 1,10-phenanthroline (18.0 mg, 0.10 mmol), P(p-Tol) 3 (18.0 mg, 0.06 mmol) and a solution of 4-methylphenyl trifluoromethanesulfonate (2a) (480 mg, 2.00 mmol) and the internal standard n-tetradecane (50 µl) in NMP (4 ml). The residue was again purified by column chromatography (Si 2, ethyl acetate/hexane gradient), yielding the corresponding biaryl. Method C (Table 3). Method C is based on Method A but performing the reaction using 8 ml of NMP. The following amounts were used: potassium 3-nitrobenzoate (1a) (205.2 mg, 0 mmol), copper(i) oxide (10.7 mg, mmol), palladium(ii) iodide (10.8 mg, 0.03 mmol), 1,10-phenanthroline (27.0 mg, 0.15 mmol) and Tol-BINAP (30.5 mg, mmol) and a solution of the triflate (2b-c) (2.00 mmol) and the internal standard n- tetradecane (50 µl) in NMP (8 ml). The residue was again purified by column chromatography (Si 2, ethyl acetate/hexane gradient), yielding the corresponding biaryl. Method D (Table 3). Method D is based on Method B but performing the reaction during 1 h. The following amounts were used: potassium 2-nitrobenzoate (1o) (205.2 mg, 0 mmol), copper(i) oxide (7.2 mg, 0.05 mmol), palladium(i) iodide (7.2 mg, 0.02 mmol), S8

9 1,10-phenanthroline (18.0 mg, 0.10 mmol), P(p-Tol) 3 (18.0 mg, 0.06 mmol) and a solution of the triflate (2b, 2d-i) (2.00 mmol) and the internal standard n-tetradecane (50 µl) in NMP (4 ml). The residue was again purified by column chromatography (Si 2, ethyl acetate/hexane gradient), yielding the corresponding biaryl. Method E (Table 2). Method E is based on Method A and specially modified for microwave irradiation reactions. An oven-dried 10 ml microwave vessel was charged with potassium 3-nitrobenzoate (1a) (103 mg, 0.50 mmol), copper(i) oxide (3.6 mg, mmol), palladium(ii) iodide (3.6 mg, 0.01 mmol), 1,10-phenanthroline (9.0 mg, 0.05 mmol) and Tol- BINAP (10.2 mg, mmol). The reaction vessel was evacuated and flushed with argon three times. Subsequently, a solution of 4-methylphenyl trifluoromethanesulfonate (2a) (120 mg, 0.50 mmol) and the internal standard n-tetradecane (50 µl) in NMP (1 ml) was added via syringe. The resulting solution was then stirred for 5 minutes at 50 ºC followed by microwave irradiation at 190 ºC for 650 seconds. The pressure noted at this temperature was 4.5 bar. The mixture was then diluted with aqueous HCl (1N, 10 ml) and extracted with ethyl acetate (3 x 20.0 ml). The combined organic layers were washed with water and brine, dried over MgS 4, filtered, and the volatiles were removed in vacuo. The residue was purified by column chromatography (Si 2, ethyl acetate/hexane gradient), yielding 3aa as a pale yellow solid (65.4 mg, 61 %). Synthesis of 4-methyl-3 -nitrobiphenyl (3aa). Compound 3aa was prepared following Method A from potassium 3-nitrobenzoate (1a) (205 mg, 0 mmol) yielding 3aa as a pale yellow solid (153 mg, 72 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-methyl-3 -nitrobiphenyl [CAS: ]. Compound 3aa was also prepared following Method E in 61 % yield (65.4 mg). S9

10 Synthesis of 4-methyl-4 -nitrobiphenyl (3ba). Compound 3ba was prepared following Method A from potassium 4-nitrobenzoate (1b) (205 mg, 0 mmol) yielding 3ba as a white solid (146 mg, 68 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-methyl-4 -nitrobiphenyl [CAS: ]. Synthesis of 3-cyano-4 -methylbiphenyl (3ca). Compound 3ca was prepared following Method A from potassium 3-cyanobenzoate (1c) (185 mg, 0 mmol) yielding 3ca as a pale yellow solid (100 mg, 52 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3-cyano-4 -methylbiphenyl [CAS: ]. Synthesis of 4-cyano-4 -methylbiphenyl (3da). Compound 3da was prepared following Method A from potassium 4-cyanobenzoate (1d) (185 mg, 0 mmol) yielding 3da as a pale yellow solid (112 mg, 58 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-cyano-4 -methylbiphenyl [CAS: ]. Synthesis of 3,4'-dimethyl-4-nitrobiphenyl (3ea). Compound 3ea was prepared following Method A from potassium 3-methyl-4-nitrobenzoate (1e) (197 mg, 0 mmol) yielding 3ea as a yellow solid (142 mg, 62 %). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 1H), (m, 2H), (m, 2H), 7.28 (d, J = 7.9 Hz, 2H), 2.67 (s, 3H), 2.41 (s, 3H) ppm; 13 C NMR (151 MHz, CDCl 3 ): δ = 147.6, 145.9, 138.7, 135.8, 134.3, 13, 129.7, 127.1, 125.4, 125.1, 21.1, 2 ppm. Anal. Calcd for C 14 H 13 N 2 : C, 74.0; H, 5.8; N, ound: C, 73.8; H, 5.8; N, 6.00 MS (Ion trap, EI): m/z (%) = 227 (100, [M+]), 210 (92), 182 (35), 167 (38), 166 (22), 165 (49), 155 (25). Synthesis of 3-chloro-4 -methylbiphenyl (3fa). Compound 3fa was prepared following Method A from potassium 3-chlorobenzoate (1f) (228 mg, 0 mmol) yielding 3fa as colorless oil (80.0 mg, 40 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3-chloro-4 -methylbiphenyl [CAS: ]. Synthesis of N-(4 -methyl-biphenyl-4-yl)-acetamide (3ga). Compound 3ga was prepared following Method A from potassium 4-acetamidobenzoate (1g) (217 mg, 0 mmol) yielding S10

11 3ga as a white solid (119 mg, 53 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for N-(4 -methyl-biphenyl-4-yl)-acetamide [CAS: ]. Synthesis of 3-(4-methylphenyl)pyridine (3ha). Compound 3ha was prepared following Method A from potassium nicotinate (1h) (161 mg, 0 mmol) yielding 3ha as a colorless oil (69.1 mg, 41 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3-(4-methylphenyl)pyridine [CAS: ]. Synthesis of 3-(4-methylphenyl)thiophene (3ia). Compound 3ia was prepared following Method A from potassium thiophene-3-carboxylate (1i) (166 mg, 0 mmol), yielding 3ia as a white solid (94 mg, 54 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3-(4-methylphenyl)thiophene [CAS: ]. Synthesis of 2-fluoro-4'-methylbiphenyl (3ja). Compound 3ja was prepared following Method A from potassium 2-fluorobenzoate (1j) (178 mg, 0 mmol) yielding 3ja as a colorless oil (141 mg, 76 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-fluoro-4'-methylbiphenyl [CAS: ]. Synthesis of 2-acetyl-4'-methylbiphenyl (3ka). Compound 3ka was prepared following Method A from potassium 2-acetylbenzoate (1k) (190 mg, 0 mmol) yielding 3ka as a white solid (168 mg, 80 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-acetyl-4'-methylbiphenyl [CAS: ]. Synthesis of 2-methoxy-4'-methylbiphenyl (3la). Compound 3la was prepared following Method A from potassium 2-methoxybenzoate (1l) (190 mg, 0 mmol) yielding 3la as a pale yellow solid (80.5 mg, 40 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-methoxy-4'-methylbiphenyl [CAS: ]. Synthesis of 2-(4-methylphenyl)thiophene (3ma). Compound 3ma was prepared following Method B from potassium thiophene-2-carboxylate (1m) (166 mg, 0 mmol) yielding 3ma as a white solid (130 mg, 75 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-(4-methylphenyl)thiophene [CAS: ]. S11

12 Synthesis of 2-(4-methylphenyl)furan (3na). Compound 3na was prepared following Method B from potassium furan-3-carboxylate (1n) (150 mg, 0 mmol) yielding 3na as a yellow oil (119 mg, 75 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3-(4-methylphenyl)furan [CAS: ]. Synthesis of 4-methyl-2 -nitrobiphenyl (3oa). Compound 3oa was prepared following Method B from potassium 2-nitrobenzoate (1o) (205 mg, 0 mmol) yielding 3oa as a yellow oil (193 mg, 91 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-methyl-2 -nitrobiphenyl [CAS: ]. Synthesis of 2-(3-nitrophenyl)naphthalene (3ab). Compound 3ab was prepared following Method C from 2-naphthyl trifluoromethanesulfonate (2b) (552 mg, 2.00 mmol) yielding 3ab as a yellow solid (154 mg, 62 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-(3-nitrophenyl)-naphthalene [CAS: ]. Synthesis of 3-acethyl-3 -nitrobiphenyl (3ac). Compound 3ac was prepared following Method C from 3-acethylphenyl trifluoromethanesulfonate (2c) (536 mg, 2.00 mmol) yielding 3ai as a yellow solid (135 mg, 58 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 3-acethyl-3 -nitrobiphenyl [CAS: ]. Synthesis of 2-(2-nitrophenyl)naphthalene (3ob). Compound 3ob was prepared following Method D from 2-naphthyl trifluoromethanesulfonate (2b) (552 mg, 2.00 mmol) yielding 3ob as a yellow solid (243 mg, 98 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-(2-nitrophenyl)-naphthalene [CAS: ]. Synthesis of 2-nitrobiphenyl (3od). Compound 3od was prepared following Method D from phenyl trifluoromethanesulfonate (2d) (452 mg, 2.00 mmol), yielding 3od as a yellow oil (181 mg, 91 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-nitrobiphenyl [CAS: ]. Synthesis of 4-methoxy-2 -nitrobiphenyl (3oe). Compound 3oe was prepared following Method D from 4-methoxyphenyl trifluoromethanesulfonate (2e) (512 mg, 2.00 mmol) S12

13 yielding 3oe as a yellow solid (189 mg, 83 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-methoxy-2 -nitrobiphenyl [CAS: ]. Synthesis of 2-methyl-2 -nitrobiphenyl (3of). Compound 3of was prepared following Method D from 2-methylphenyl trifluoromethanesulfonate (2f) (480 mg, 2.00 mmol) yielding 3of as a yellow oil (166 mg, 79 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 2-methyl-2 -nitrobiphenyl [CAS: ]. Synthesis of 1-(2'-nitrobiphenyl-4-yl)propan-1-one (3og). Compound 3og was prepared following Method D from 4-propionylphenyl trifluoromethanesulfonate (2g) (564 mg, 2.00 mmol) yielding 3og as a yellow solid (116 mg, 45 %). 1 H NMR (600 MHz, CDCl 3 ): δ = 8.02 (d, J = 8.4 Hz, 2H), 7.92 (dd, J =8.1, 0.9 Hz, 1H), 7.65 (td, J = 7.6, Hz, 1H), 7.53 (td, J = 7.8, 1.3 Hz, 1H), 7.43 (dd, J = 7.7, Hz, 1H), 7.40 (d, J = 8.4 Hz, 2H), 3.03 (q, J = 7.2 Hz, 2H), 1.24 (t, J = 7.2 Hz, 3H) ppm; 13 C NMR (151 MHz, CDCl 3 ): δ = 200.1, 148.9, 142.0, 136.4, 135.5, 132.6, 131.7, 128.8, 128.3, 128.2, 124.4, 31.9, 8.2 ppm. Anal. Calcd for C 15 H 13 N 3 : C, 70.6; H, 5.13; N, ound: C, 70.7; H, 5.3, N, MS (Ion trap, EI): m/z (%) = 255 (3, [M+]), 227 (19), 226 (100), 180 (11), 152 (12). Synthesis of 4-chloro-2 -nitrobiphenyl (3oh). Compound 3oh was prepared following Method D from 4-chlorophenyl trifluoromethanesulfonate (2h) (521 mg, 2.00 mmol) yielding 3oh as a yellow solid (211.5 mg, 91 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for 4-chloro-2 -nitrobiphenyl [CAS: ]. Synthesis of 8-(2 -nitrophenyl)-quinoline (3oi). Compound 3oi was prepared following Method D from quinoline-8-yl trifluoromethanesulfonate (2i) (554 mg, 2.00 mmol) yielding 3oi as a yellow solid (200 mg, 80 %). The spectroscopic data (NMR, GC-MS) matched those reported in the literature for Synthesis of 8-(2 -nitrophenyl)-quinoline [CAS: ]. S13

14 Potassium 3-nitrobenzoate (1a) 1 H NMR (, 600 MHz) K N C NMR (, 151 MHz) S14

15 Potassium 4-nitrobenzoate (1b) 1 H NMR (D 2, 400 MHz) Deuterium xide - N + - K C NMR (D 2, 101 MHz) S15

16 Potassium 3-cyanobenzoate (1c) 1 H NMR (, 600 MHz) K N C NMR (, 151 MHz) K N M04 M06 M05 M S16

17 Potassium 4-cyanobenzoate (1d) 1 H NMR (, 600 MHz) K N C NMR (, 151 MHz) K N S17

18 Potassium 3-methyl-4-nitrobenzoate (1e) 1 H NMR (, 600 MHz) 2.56 K - N C NMR (, 151 MHz) K - N S18

19 Potassium 3-chlorobenzoate (1f) 1 H NMR (, 600 MHz) 7.81 K 7.21 Cl C NMR (, 151 MHz) K Cl S19

20 Potassium 4-acetamidobenzoate (1g) 1 H NMR (, 600 MHz) 2.00 K H 3 C NH C NMR (, 151 MHz) K H 3 C NH S20

21 Potassium nicotinate (1h) 1 H NMR (, 600 MHz) K N C NMR (, 151 MHz) K N S21

22 Potassium thiophene-3-carboxylate (1i) 1 H NMR (, 600 MHz) S K 13 C NMR (, 151 MHz) K S S22

23 Potassium 2-fluorobenzoate (1j) 1 H NMR (, 400 MHz) K C NMR (, 101 MHz) K S23

24 Potassium 2-acetylbenzoate (1k) 1 H NMR (, 600 MHz) 2.43 K C NMR (, 151 MHz) K S24

25 Potassium 2-metoxybenzoate (1l) 1 H NMR (, 600 MHz) 3.82 K C NMR (, 151 MHz) K S25

26 Potassium thiophene-2-carboxylate (1m) 1 H NMR (D 2, 200 MHz) (4,6) (7) 6 7 S K Deuterium xide C NMR (D 2, 151 MHz) S K S26

27 Potassium furan-2-carboxylate (1n) 1 H NMR (, 600 MHz) K C NMR (, 151 MHz) K S27

28 Potassium 2-nitrobenzoate (1o) 1 H NMR (, 400 MHz) N + - K C NMR (, 101 MHz) K N S28

29 4-Methylphenyl trifluoromethanesulfonate (2a) 1 H NMR (CDCl 3, 400 MHz) 2.41 S C NMR (CDCl 3, 101 MHz) S S29

30 2-Naphthyl trifluoromethanesulfonate (2b) 1 H NMR (CDCl 3, 600 MHz) M S C NMR (CDCl 3, 151 MHz) S S30

31 3-Acethylphenyl trifluoromethanesulfonate (2c) 1 H NMR (CDCl 3, 200 MHz) 2.62 S M C NMR (CDCl 3, 50 MHz) S S31

32 Phenyl trifluoromethanesulfonate (2d) 1 H NMR (CDCl 3, 600 MHz) S C NMR (CDCl 3, 151 MHz) S S32

33 4-Methoxyphenyl trifluoromethanesulfonate (2e) 1 H NMR (CDCl 3, 600 MHz) 3.81 S C NMR (CDCl 3, 151 MHz) S S33

34 2-Methylphenyl trifluoromethanesulfonate (2f) 1 H NMR (CDCl 3, 400 MHz) 2.43 H 3 C S C NMR (CDCl 3, 101 MHz) H 3 C S S34

35 4-Propionylphenyl trifluoromethanesulfonate (2g) 1 H NMR (CDCl 3, 600 MHz) 1.22 S C NMR (CDCl 3, 151 MHz) S S35

36 4-Chlorophenyl trifluoromethanesulfonate (2h) 1 H NMR (CDCl 3, 600 MHz) Cl S C NMR (CDCl 3, 151 MHz) Cl S S36

37 2-Quinolyl trifluoromethanesulfonate (2i) 1 H NMR (CDCl 3, 600 MHz) N 7.51 S M M C NMR (CDCl 3, 151 MHz) N S S37

38 4-Methyl-3 -nitrobiphenyl (3aa) 1 H NMR (CDCl 3, 400 MHz) N M06 M05 M C NMR (CDCl 3, 101 MHz) - N S38

39 4-Methyl-4 -nitrobiphenyl (3ba) 1 H NMR (CDCl 3, 600 MHz) N M C NMR (CDCl 3, 151 MHz) N S39

40 3-Cyano-4 -methylbiphenyl (3ca) 1 H NMR (CDCl 3, 600 MHz) 2.41 N M05 M06 M C NMR (CDCl 3, 151 MHz) N S40

41 4-Cyano-4 -methylbiphenyl (3da) 1 H NMR (CDCl 3, 600 MHz) 2.41 N M C NMR (CDCl 3, 151 MHz) N S41

42 3,4 -Dimethyl-4-nitrobiphenyl (3ea) 1 H NMR (CDCl 3, 600 MHz) N M C NMR (CDCl 3, 151 MHz) C H N S42

43 3-Chloro-4 -methylbiphenyl (3fa) 1 H NMR (CDCl 3, 400 MHz) 2.47 Cl M04 M C NMR (CDCl 3, 101 MHz) Cl S43

44 N-(4 -methyl-biphenyl-4-yl)-acetamide (3ga) 1 H NMR (CDCl 3, 600 MHz) H 3 C NH M M05 M C NMR (CDCl 3, 151 MHz) M04 M H 3 C NH M M09 M07 M S44

45 3-(4-Methylphenyl)pyridine (3ha) 1 H NMR (CDCl 3, 600 MHz) 2.39 N 8.83 M05 M C NMR (CDCl 3, 151 MHz) N S45

46 3-(4-Methylphenyl)thiophene (3ia) 1 H NMR (CDCl 3, 400 MHz) 2.45 S M04 M C NMR (CDCl 3, 101 MHz) S S46

47 2-luoro-4 -methylbiphenyl (3ja) 1 H NMR (CDCl 3, 600 MHz) 2.44 M05 M04 M C NMR (CDCl 3, 151 MHz) S47

48 2-Acetyl-4 -methylbiphenyl (3ka) 1 H NMR (CDCl 3, 400 MHz) M04 M C NMR (CDCl 3, 101 MHz) S48

49 2-Methoxy-4 -methylbiphenyl (3la) 1 H NMR (CDCl 3, 600 MHz) M07M04 M06 M C NMR (CDCl 3, 151 MHz) S49

50 2-(4-Methylphenyl)thiophene (3ma) 1 H NMR (CDCl 3, 600 MHz) 2.46 S M04 M C NMR (CDCl 3, 151 MHz) S S50

51 2-(4-Methylphenyl)furan (3na) 1 H NMR (CDCl 3, 600 MHz) M C NMR (CDCl 3, 151 MHz) S51

52 4-Methyl-2 -nitrobiphenyl (3oa) 1 H NMR (CDCl 3, 600 MHz) N M C NMR (CDCl 3, 151 MHz) N S52

53 2-(3-Nitrophenyl)naphthalene (3ab) 1 H NMR (CDCl 3, 400 MHz) M07 M M M N C NMR (CDCl 3, 101 MHz) N S53

54 3-Acethyl-3 -nitrobiphenyl (3ac) 1 H NMR (CDCl 3, 400 MHz) 2.67 N + - M06 M07 M05M C NMR (CDCl 3, 101 MHz) N S54

55 2-(2-Nitrophenyl)naphthalene (3ob) 1 H NMR (CDCl 3, 400 MHz) M05 M N C NMR (CDCl 3, 151 MHz) N S55

56 2-Nitrobiphenyl (3od) 1 H NMR (CDCl 3, 400 MHz) 7.45 N M C NMR (CDCl 3, 151 MHz) N S56

57 4-Methoxy-2 -nitrobiphenyl (3oe) 1 H NMR (CDCl 3, 400 MHz) 3.87 N + - M04 M C NMR (CDCl 3, 101 MHz) N S57

58 2-Methyl-2 -nitrobiphenyl (3of) 1 H NMR (CDCl 3, 400 MHz) 2.15 H 3 C N + - M M06 M M C NMR (CDCl 3, 151 MHz) H 3 C N S58

59 1-(2 -Nitrobiphenyl-4-yl)propan-1-one (3og) 1 H NMR (CDCl 3, 600 MHz) 1.24 M04 N + M05 M M C NMR (CDCl 3, 151 MHz) N + - M06 M08 M04 M09 M M M M S59

60 4-Chloro-2 -nitrobiphenyl (3oh) 1 H NMR (CDCl 3, 600 MHz) Cl N M C NMR (CDCl 3, 151 MHz) Cl N S60

61 8-(2 -Nitrophenyl) quinoline (3oi) 1 H NMR (CDCl 3, 600 MHz) N + - M04 M M06 M N C NMR (CDCl 3, 151 MHz) N + - N S61