Supporting Information

Supporting Information Phosphane-free Suzuki Miyaura Coupling of Aryl Imidazolesulfonates with Arylboronic Acids and Potassium Aryltrifluoroborates under Aqueous Conditions José Francisco Cívicos, Mohammad Gholinejad, Diego A. Alonso,* and Carmen Nájera* Departamento de Química Orgánica and Instituto de Síntesis Orgánica, Universidad de Alicante, Apdo. 99, E-03080, Alicante, Spain (Received March 8, 2011; CL-110199; E-mail: diego.alonso@ua.es, cnajera@ua.es) Copyright The Chemical Society of Japan

1. General.3 2. Synthesis of 1,1 -Sufonyldiimidazole...3 3. Synthesis of tert-butyl naphthalen-1-yl Carbonate (2aa).. 3 4. Synthesis of Naphthalene-1-yl Dimethylcarbamate (2ab).4 5. Synthesis of Naphthalen-2-yl Bis(2-oxooazolidin-3-yl)phosphinate (2ac)..4 6. Synthesis of Naphthalene-1-yl Dimethylsulfamate (2ad)..5 7. Typical Procedure for the Synthesis of Aryl Imidazolylsulfonates 5 8. Typical Procedure for the Suzuki Coupling with Conventional Heating...5 9. Typical Procedure for MW Suzuki Coupling 6 10. Typical Procedure for the One Pot Suzuki Coupling 6 11. Physical and spectroscopic data.7 12. References.14 13. 1 H-NMR and 13 C-NMR spectra 15 2

1. General Unless otherwise noted all commercial reagents and solvents were used without further purification. Melting points were determined with a Reichert Thermovar hot plate apparatus and are uncorrected. IR spectra were recorded on a Nicolet 510 P- FT. 1 H-NMR (300 or 400 MHz) and 13 C-NMR (75 or 100 MHz) spectra were obtained on a Bruker AC-300 and Bruker AC-400, respectively, using CDCl 3 as solvent and TMS as internal standard, unless otherwise stated. Low-resolution electron impact (EI) mass spectra were obtained at 70 ev on an Agilent 5973 Network Mass selective detector. Analytical TLC was performed on Merck aluminum sheets with silica gel 60 F 254. Silica gel 60, (0.04-0.06 mm) was employed for flash chromatography. Microwave reactions were performed with a CEM Discover Synthesis Unit (CEM Corp., Matthews, NC) with a continuous focused microwave power delivery system in glass vessels (10 ml) sealed with a septum under magnetic stirring. The temperature of the reaction mixture inside the vessel was monitored using a calibrated infrared temperature control under the reaction vessel. 2. Synthesis of 1,1 -Sufonyldiimidazole. 1 To a 0 ºC solution of imidazole (20.0 g, 294 mmol) in anhydrous CH 2 Cl 2 (210 ml), cooled to 0ºC, was added a solution of sulfuryl chloride (5.0 ml, 61.6 mmol) in anhydrous CH 2 Cl 2 (28 ml), drop-wise. The reaction mixture was allowed to warm to ambient temperature and stirred for 16 hours. The reaction mixture was filtered, the solvent evaporated under reduced pressure, and the resulting solid crystallized from isopropyl alcohol (100 ml). The obtained white needles were filtered, washed with cold isopropyl alcohol and dried under reduced pressure to afford 10.59 g of pure 1,1 sulfonyldiimidazole (87%). 3. Synthesis of tert-butyl Naphthalen-1-yl Carbonate (2aa). Under Ar atmosphere, a 100 ml round bottom flask was charged with 1- naphthol (1 g, 6.94 mmol, 1 equiv), DMAP (0.086 g, 0.694 mmol, 0.1 equiv), Et 3 N (1.07 ml, 7.64 mmol, 1.1 equiv) and anhydrous CH 2 Cl 2 (23 ml). Then, a solution of Boc 2 O (1.66 g, 7.46 mmol, 1.1 equiv) in anhydrous CH 2 Cl 2 (10 ml) was added dropwise via cannula. The resulting solution was stirred during 15 min. Then, the solution was transferred to a separatory funnel and NaHSO 4 (20 ml, 0.5 M) was added. The layers were separated and the aqueous layer was washed with CH 2 Cl 2 (3 20 ml), washed with brine (20 ml), dried over MgSO 4, and concentrated under reduced pressure. The 3

crude residue was purified by flash chromatography (Hexane/EtOAc: 3/1) to obtain 1.61 g of compound 2aa (95% yield). 4. Synthesis of Naphthalene-1-yl Dimethylcarbamate (2ab). Under Ar atmosphere, a round bottom flask charged with NaH (0.4 g, 16.67 mmol, 1.2 equiv, 60% dispersion in oil), cooled to 0ºC. Then, a solution of 1-naphthol (2 g, 13.88 mmol, 1 equiv) in anhydrous DME (45 ml) was added dropwise via cannula. The resulting solution was stirred at r.t. for 10 min, and then cooled to 0 ºC. A solution of dimethyl carbamoyl chloride (1.80 g, 16.76 mmol, 1.2 equiv) in anhydrous DME (10mL) was then added dropwise via cannula to the vessel. The reaction was warmed to rt, allowed to stir for 11 h, and then quenched with water. The solvent was removed under reduced pressure, and the solid material was dissolved in Et 2 O (50 ml) and H 2 O (15 ml), and transferred to a separatory funnel. The layers were separated, and the organic layer was washed with 1 M KOH (15 ml), then H 2 O (15 ml). The combined aqueous layers were extracted with Et 2 O (3 20 ml), washed with brine (15 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (Hexane/EtOAc: 4/1) to obtain 2.75 g of compound 2ab (92% yield). 5. Synthesis of Naphthalen-2-yl Bis(2-oxooazolidin-3-yl)phosphinate (2ac). Under Ar atmosphere, a 100 ml round bottom flask was charged with 2- naphthol (0.2 g, 1.39 mmol, 1 equiv), bis(2-oxo-3-oxazolidinyl)phosphinic chloride (0.35 g, 1.39 mmol, 1 equiv) and anhydrous CH 2 Cl 2 (7 ml). The obtained mixture was cooled to 0 ºC. Then, Et 3 N (0.19 ml, 1.39 mmol, 1 equiv) was added dropwise. The reaction was allowed to stir to r.t. Then, the reaction mixture was transferred to a separatory funnel and NaHSO 4 (20 ml, 0.5 M) was added. The layers were separated and the aqueous layer was washed with EtOAc. The combined organic layers were then washed with brine (20 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography to obtain 0.311 g of compound 2ac (62% yield). 4

6. Synthesis of Naphthalene-1-yl Dimethylsulfamate (2ad). Under Ar atmosphere, a 100 ml round bottom flask was charged with NaH (0.4 g, 16.67 mmol, 1.2 equiv, 60% dispersion in oil), was cooled to 0 ºC. Then, a solution of 1-naphthol (2 g, 13.88 mmol, 1 equiv) in anhydrous DME (45 ml) was added dropwise via cannula. The resulting solution was stirred at r.t. for 10 min, and then cooled back to 0 ºC. A solution of dimethyl sulfamoyl chloride (2.39 g, 16.67 mmol, 1.2 equiv) in anhydrous DME (10 ml) was then added dropwise via cannula to the vessel. The reaction was warmed to rt, allowed to stir for 11 h, and then quenched carefully with water. The solvent was removed under reduced pressure, and the solid material was dissolved in Et 2 O (50 ml) and H 2 O (15 ml), and transferred to a separatory funnel. The layers were separated, and the organic layer was washed in this order, with 1 M KOH (15 ml), and H 2 O (15 ml). The combined aqueous layers were extracted with Et 2 O (3 20 ml). The combined organic layers were then washed with brine (15 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (Hexane/EtOAc: 4/1) to obtain 2.54 g of compound 2ad (85% yield). 7. Typical Procedure for the Synthesis of Aryl Imidazolylsulfonates. A 100 ml round bottom flask was charged with 1-naphthol (1 g, 6.94 mmol, 1 equiv), 1,1 -N,N -sulfonyldiimidazole (2.75 g, 13.88 mmol, 2 equiv), and cesium carbonate (1.13 g, 3.47 mmol, 0.5 equiv) in THF (20 ml). The reaction was stirred at r.t. for 4-16 h. When the reaction was complete (TLC), the solvent was evaporated and EtOAc was added to the obtained a solution wwhich was cooled at 0 ºC. Then a saturated aqueous NH 4 Cl was added. The layers were separated and the aqueous layer was washed with EtOAc (2 20 ml). The combined organic extracts were washed with water (1 20 ml), followed by brine (1 20 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography. 8. Typical Procedure for the Suzuki Coupling with Conventional Heating. A 10 ml round bottom flask was charged with naphthalen-1-yl-1h-imidazole-1- sulfonate (0.024 g, 0.1 mmol, 1 equiv), 4-tolylboronic acid (0.020 g, 0.15 mmol, 1.5 equiv), KOH (0.011 g, 0.2 mmol, 2 equiv), TBAB (0.016 g, 0.05 mmol, 20 mol%) catalyst 1a (0.00029 g, 1 mol% Pd) a MeOH/H 2 O mixture (3/1, 4 ml). The reaction was 5

allowed to stir at 110 ºC, during 24 h. Then, the solution was transferred to a separatory funnel. The layers were separated, and the aqueous layer was extracted with EtOAc (3 10 ml). The organic layers were washed with H 2 O (3 10 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (EtOAc/hexane: 4/1) to obtain 0.017 g of the corresponding pure coupling compound 3b in 90% yield. 9. Typical Procedure for MW Suzuki Coupling. A 10 ml MW vessel was charged with naphthalen-1-yl-1h-imidazole-1- sulfonate (0.024 g, 0.1 mmol, 1 equiv), phenylboronic acid (0.018 g, 0.15 mmol), KOH (0.011 g, 0.2 mmol), TBAB (0.016 g, 0.05 mmol), catalyst 1b (0.00041 g, 1 mol % Pd), a MeOH/H 2 O mixture (3/1, 2 ml) were added. The vessel was sealed with pressure lock, and the mixture was heated in air at 110 ºC by a MW irradiation of 40 W for 30 min in a CEM Discover MW reactor. The reaction mixture was extracted with EtOAc (3 10 ml), and the organic layers were washed with H 2 O (3 10 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (EtOAc/hexane: 3/1) to obtain 0.018 g of the corresponding pure coupling compound 3a in 99% yield. 10. Typical Procedure for the One Pot Suzuki Coupling. A 10 ml round bottom flask was charged with 1-napthol (0.144 g, 1 mmol), Cs 2 CO 3 (0.163 g, 0.5 mmol), 1,1 -sulfonyldiimidazole (0.297 g, 1.5 mmol) and THF (5 ml). The reaction was stirred until completion (monitored by TLC). Then the solvent was evaporated and in the same reaction flask phenylboronic acid (0.183 g, 1.5 mmol), KOH (0.112 g, 2 mmol), TBAB (0.006 g, 0.02 mmol), catalyst 1b (0.0041 g, 1 mol % Pd) a MeOH/H 2 O mixture (3/1, 4 ml) were added. After 24 h, the reaction mixture was extracted with EtOAc (3 10 ml), and the organic layers were washed with H 2 O (3 10 ml), dried over MgSO 4, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (EtOAc/hexane: 3/1) to obtain 0.145 g of the corresponding pure coupling compound 3a in 71% yield. 6

11. Physical and spectroscopic data: tert-butyl Naphthalen-1-yl Carbonate (2aa). 2 Yield 95%; Yellow oil; R f 0.91 (hexane/etoac: 3/1); IR (neat) υ (cm -1 ) 3059, 2981, 2934, 2872, 1760, 1739, 1600, 1510, 1462, 1393, 1371, 1274, 1256, 1229, 1142, 1093, 1047, 784, 772; δ H (400 MHz) 7.97-7.95 (m, 1H), 7.86 (dd, J = 7.2, 2.8 Hz, 1H), 7.73 (d, J = 8.4 Hz, 1H), 7.55-7.48 (m, 2H), 7.46 (t, J = 8 Hz, 1H), 7.31 (dd, J = 7.6, 0.8 Hz, 1H), 1.59 (s, 9H); δ C 151.8, 146.7, 134.4, 127.7, 126.7, 126.20, 126.16, 125.7, 125.1, 120.8, 117.5, 83.2, 27.4; MS (m/z, %) 245 (M + +1, 18), 244 (M +, 100), 185 (17), 145 (31), 144 (100), 127 (36), 116 (14), 115 (85), 89 (11), 57 (100). Naphthalene-1-yl Dimethylcarbamate (2ab). 2 Yield 92%; Pale brown solid; m.p. 73-74 C (hexane); R f 0.59 (hexane/etoac: 4/1); IR (neat) υ (cm -1 ) 3053, 2932, 1727, 1595, 1486, 1461, 1378, 1256, 1228, 1162, 1078, 1044, 1018, 994, 868, 797, 769; δ H 7.93 (dd, J = 9, 3 Hz, 1H), 7.86-7.83 (m, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.50-7.42 (m, 3H), 7.28 (dd, J = 7.5, 0.9 Hz, 1H), 3.24 (s, 3H), 3.06 (s, 3H); δ C 154.8, 147.2, 134.5, 127.8, 127.3, 126.2, 125.4, 125.3, 121.2, 118.1, 36.8, 36.5; MS (m/z, %) 216 (M + +1, 23), 215 (M +, 100), 143 (10), 127 (21), 116 (13), 115 (100), 89 (21), 73 (21), 72 (100), 63 (16). 7

Naphthalen-2-yl Bis(2-oxooazolidin-3-yl)phosphinate (2ac). 3 Yield 62%; White solid; m.p. 285-286 C (hexane); IR (neat) υ (cm -1 ) 3497, 3414, 3055, 3021, 2932, 1774, 1633, 1598, 1509, 1487, 1482, 1390, 1384, 1294, 1202, 1158, 982, 764, 611; δ H 7.86 (dd, J = 8.8, 5.2 Hz, 3H), 7.78 (s, 1H), 7.56-7.40 (m, 2H), 7.42 (dd, J = 7.6, 1.2 Hz, 1H), 4.53-4.40 (m, 4H), 4.21 (dd, J = 8.8, 6.4 Hz, 2H), 4.1 (dd, J = 7.6, 1.6 Hz, 2H); δ C 156.1, 156.0, 146.2, 146.1, 133.7, 131.5, 130.5, 127.8, 127.7, 127.2, 126.2, 120.0, 119.9, 117.6, 117.5, 64.7, 64.6, 45.61, 45.58; MS (m/z, %) 363 (M + +1, 18), 362 (M +, 100), 281 (21), 213 (33), 208 (14), 207 (58), 191 (11), 190 (10), 169 (20), 168 (19), 167 (10), 154 (26), 144 (25), 141 (12), 127 (25), 115 (44), 77 (10), 73 (10). Naphthalene-1-yl Dimethylsulfamate (2ad). 2 Yield 85%; Pale brown solid; m.p. 73-76 C (hexane); R f 0.33; IR (KBr) υ (cm -1 ) 3053, 2984, 2935, 1595, 1370, 1221, 1179, 977, 881, 809, 767, 698; δ H 8.21 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 7.6 Hz, 1H), 7.79 (d, J = 8 Hz, 1H), 7.62-7.54 (m, 3H), 7.48 (t, J = 8 Hz, 1H), 3.08 (s, 6H); δ C 146.1, 134.8, 127.9, 127.1, 126.8, 126.6, 125.4, 121.5, 117.8, 38.9; MS (m/z, %) 247 (M +, 251), 158 (10), 144 (19), 143 (72), 116 (11), 115 (100). Naphthalen-1-yl-1H-imidazole-1-sulfonate (2ae). 4 Yield 76%; White solid; m.p. 101 ºC (hexane); R f 0.39 (hexane/etoac: 2/1); IR (KBr) υ (cm -1 ) 3132, 3092, 1425, 1208, 1161, 1063, 907, 816, 773, 624; δ H 7.91-7.79 (m, 4H), 7.60-7.55 (m, 2H), 7.42 (t, J = 7.8 Hz, 1H), 7.32 (s, 1H), 7.13 (s, 1H), 7.01 (d, J = 7.5 Hz, 1H); δ C 145.3, 137.4, 134.8, 131.3, 128.7, 128.0, 127.7, 127.4, 126.4, 125.1, 120.4, 118.4, 117.8; MS (m/z, %) 274 (M +, 56), 144 (15), 143 (86), 116 (11), 115 (100). Phenyl-1H-imidazole-1-sulfonate (2be). 5 Yield 98%; Colorless oil; R f 0.34 (hexane/etoac: 3/1); IR (neat) υ (cm -1 ) 3125, 1585, 1524, 1485, 1420, 1204, 1135, 8

1050, 877, 784, 688; δ H 7,73 (s, 1H), 7.41-7.35 (m, 3H), 7.31 (s, 1H), 7.17 (s, 1H), 6.97-6.90 (m, 2H); δ C 149.0, 137.5, 131.4, 130.3, 128.7, 121.3, 118.3; MS (m/z, %) 225 (M + +1, 10), 224 (M +, 78), 144 (16), 132 (15), 131 (12), 117 (70), 94 (77), 93 (59), 77 (15), 67 (10), 65 (100). Me OSO 2 Im p-tolyl-1h-imidazole-1-sulfonate (2ce). 5 Yield 86%; Pale yellow oil; R f 0.32 (hexane/etoac: 4/1); IR (neat) υ (cm -1 ) 3427, 3130, 2927, 1598, 1524, 1502, 1459, 1427, 1345, 1208, 1160, 1159, 1096, 1051, 995, 882, 830, 611; δ H 7.71 (s, 1H), 7.29 (s, 1H), 7.15 (dd, J = 9.6, 2.4 Hz, 3H), 6.80 (dd, J = 6.8, 1.6 Hz, 2H), 2.34 (s, 3H); δ C 146.9, 138.7, 137.5, 131.2, 130.7, 120.9, 118.3, 20.9; MS (m/z, %) 238 (M +, 50), 158 (14), 131 (31), 108 (32), 107 (100), 79 (38), 78 (14), 77 (49). 3,5-Dimethylphenyl-1H-imidazole-1-sulfonate (2de). Yield 90%; Colorless solid; m.p. 47-48 ºC (hexane); R f 0.32 (hexane/etoac: 3/1); IR (KBr) υ (cm -1 ) 3407, 3156, 3133, 2923, 2252, 1618, 1589, 1428, 1205, 1158, 1118, 1052, 908, 732; ; δ H 7.74 (s, 1H), 7.30 (d, J = 1.2 Hz, 1H), 7.16 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 6.51 (s, 2H), 2.26 (s, 3H); δ C 148.9, 140.3, 137.5, 131.0, 130.0, 118.5, 118.3, 21.0; MS (m/z, %) 253 (M + +1,22), 252 (M +, 100), 188 (55), 187 (16), 160 (20), 159 (27), 146 (15), 145 (48), 132 (10), 122 (83), 121 (100), 120 (18), 107 (15), 105 (13), 103 (10), 93 (71), 92 (100), 91 (100), 79 (15), 78 (28), 77 (100), 69 (11), 67 (19), 65 (23), 53 (22), 51 (16). HRMS calcd for C 11 H 12 N 2 O 3 S 252.0569 found 252.0561. 4-(Trifluoromethyl)phenyl-1H-imidazole-1-sulfonate (2ee). Yield 76%; Colorless oil; R f 0.37 (hexane/etoac: 3/1); IR (neat) υ (cm -1 ) 3405, 2922, 2852, 1614, 1424, 1416, 1325, 1211, 1165, 1144, 1065, 1058; δ H 7.78 (s, 1H), 7.67 (d, J = 8.7 Hz, 2H), 7.33 (s, 1H), 7.21 (s, 1H), 7.08 (d, J = 9 Hz, 2H); δ C 150.9, 137.4, 131.6, 131.1 (q, J = 33.4 Hz), 127.86, 127.81, 127.77 (q, J = 3.5 Hz), 127.71, 123.1 (q, J = 272 Hz), 122.1, 118.3, 9

115.4; MS (m/z, %) 293 (M + +1, 11), 292 (M +, 100), 273 (15), 205 (22), 200 (14), 185 (78), 173 (12), 172 (12), 162 (85), 161 (31), 145 (20), 143 (10), 133 (97), 132 (16), 131 (13), 114 (17), 113 (36), 83 (23), 67 (45), 63 (15). HRMS calcd for C 10 H 7 F 3 N 2 O 3 S 292.0129 found 292.0149. 2-(Trifluoromethyl)phenyl-1H-imidazole-1-sulfonate (2fe). Yield 73%; Light yellow oil; R f 0.50 (hexane/etoac: 2/1); IR (neat) υ (cm -1 ) 2915, 2849, 1615, 1433, 1318, 1192, 1152, 1050, 881, 779, 729; δ H 7.92 (s, 1H), 7.72 (d, J = 7.6, 1H), 7.63 (t, J = 7.2, 1H), 7.48 (t, J = 8.4, 1H), 7.35 (br.s, 1H), 7.25 (d, J = 8.4, 1H), 7.18 (br.s, 1H); δ C 146.2, 137.2, 133.9, 132.6 (q, J = 31.4 Hz), 131.4, 128.3, 128.2 (q, J = 5.2 Hz), 128.1, 123.4 (q, J = 7.8 Hz), 121.8 (q, J = 272 Hz); MS (m/z, %) 293 (M + +1, 13), 292 (M +, 100), 200 (12), 185 (75), 173 (10), 172 (10), 162 (80), 161 (26), 145 (15), 133 (86), 132 (13), 114 (14), 113 (37), 83 (23), 67 (48). HRMS calcd for C 10 H 7 F 3 N 2 O 3 S 292.0129 found 292.0156. 2,6-Dimethylphenyl-1H-imidazole-1-sulfonate (2ge). Yield 90%; White solid; m.p. 56-58 C; R f 0.42 (hexane/etoac: 3/1); IR (KBr) υ (cm -1 ) 3113, 3123, 2968, 2927, 1472, 1419, 1211, 1166, 1052, 893, 779, 624; δ H 7.91 (br.s, 1H), 7.36-7-35 (br.s, 1H), 7.22-7.06 (m, 4H); 2.08 (s, 6H), δ C 147.7, 137.0, 131.5, 131.2, 129.7, 127.8, 118.5, 16.1; MS (m/z, %) 252 (M +, 5), 172 (35), 120 (41), 91 (38), 77 (33); Calcd for C 11 H 12 N 2 O 3 S: C: 52.37, H, 4.79, N: 11.10, S: 12.71; found C: 52.48, H: 4.73; N: 10.74; S: 13.60. 1-Phenylnaphthalene (3a). 6 Yield 99%; White solid; R f 0.87 (hexane); m.p. 40-41 C (hexane); IR (KBr) υ (cm -1 ) 3056, 2952, 2925, 2848, 1724, 1593, 1493, 1397, 1277, 1069, 804, 777, 703; δ H 7.94-7.88 (m, 3H), 7.57-7.50 (m, 6H), 7.49-7.43 (m, 3H); δ C 10

140.8, 140.3, 133.8, 131.6, 130.1, 128.3, 127.6, 127.2, 126.9, 126.0, 125.8, 125.4; MS (m/z, %) 205 (M + +1, 16), 204 (M +, 98), 203 (M + -1, 100), 202 (61), 201 (11), 200 (12), 101 (18). 1-(p-Tolyl)naphthalene (3b). 6 Yield 90%; White solid; R f 0.72 (hexane); m.p. 52-53 C (hexane); IR (KBr) υ (cm -1 ) 3045, 2919, 2862, 1590, 1517, 1504, 1394, 1023, 800; δ H 8.00-7.89 (m, 3H), 7.59-7.54 (m, 2H), 7.55-7.45 (m, 4H), 7.36 (d, J = 8 Hz, 2H); 2.51 (s, 3H); δ C 140.3, 137.9, 136.9, 133.9, 131.8, 130.0, 129.5, 129.0, 128.3, 127.5, 126.9, 126.1, 125.9, 125.7, 125.4, 21.26; MS (m/z, %) 219 (M + +1, 18), 218 (M +, 100), 217 (M + -1, 31), 215 (17), 203 (60), 202 (56), 108 (11). 1-(4-Methoxyphenyl)naphthalene (3c). 7 Yield 75%; White Solid; m.p. 116 117 C (hexane); R f 0.15 (hexane); IR (KBr) υ (cm -1 ) 3043, 2990, 2995, 2825, 1607, 1502, 1390, 1242, 1168, 1102, 1028, 842, 803, 779, 568; δ H 7.96-7.92 (m, 2H), 7. 87 (d, J = 8 Hz, 1H), 7.54-7.42(m, 6H), 7.06 (d, J = 8.8 Hz, 2H), 3.92 (s, 3H); δ c 158.9, 139.9, 133.8, 133.1, 131.8, 131.1, 128.2, 127.3, 126.9, 126.1, 126.9, 125.9, 125.7, 125.4, 113.7, 55.4; MS (m/z, %) 235 (M + +1, 19), 234 (M + ), 219 (29), 191(17), 190 (23), 189 (36). 1-[4-(Trifluoromethyl]phenyl)naphthalene (3d). 8 Yield 66%; White solid; m.p. 48-49 C (hexane); R f 0.34 (hexane); IR (KBr) υ (cm -1 ) 3068, 3045, 1616, 1404, 1323, 1166, 1123, 1069, 1019, 850, 804, 700; δ H 8.09-7.99 (m, 3H), 7.90 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H), 7.69-7.57 (m, 3H), 7.54 (d, J = 8.4 Hz, 1H); δ C 144, 6, 138.6, 134.0, 131.4, 130.5, 129.6 (q, J = 32.4 Hz), 128.6, 128.5, 127.7, 127.2, 126.6, 126.2, 11

125.6, 125.5, 125.4, 125.3 (q, J = 3.4 Hz), 123.2 (q, J = 272 Hz); MS (m/z, %) 273 (M + +1, 18), 272 (M +, 100), 271 (M + -1, 23), 251 (15), 203 (50), 202 (54). 4-Methyl-1,1 -biphenyl (3e). 9 Yield 90%; White solid; m.p. 46 C (hexane); R f 0.40 (hexane); δ H 7.58 (dd, J = 8.4, 1.5 Hz, 2H), 7.49 (d, J = 8.1 Hz, 2H), 7.43 (t, J = 7.2 Hz, 2H), 7.32 (t, J = 9.3 Hz, 1H), 7.24 (d, J = 8.4 Hz, 2H), 2.39 (s, 3H); δ C 141.1, 138.3, 137.0, 129.4, 128.7, 126.9, 21.1; MS (m/z, %) 169 (M + +1, 13%), 168 (M +, 100), 167 (M + -1, 66), 164 (28), 152 (17), 151 (24). 3,5-Dimethyl-1,1 -biphenyl (3f). 10 Yield 88%; Colorless oil; R f 0.74 (hexane); IR (neat) υ (cm -1 ) 3054, 3013, 2948, 2915, 2842, 1460, 1439, 1374, 1010, 766, 705; δ H 7.62-7.55 (m, 2H), 7.47-7.30 (m, 3H), 7.23 (d, J = 14.1 Hz, 2H), 2.38 (s, 6H); δ C 141.4, 141,1, 138.2, 128.9, 128.7, 128.6, 127.22, 127.16, 127.1, 125.1, 21.4; MS (m/z, %): 183 (M + +1, 17), 182 (M +, 100), 181 (M + -1, 20), 167 (62), 166 (19), 165 (43), 152 (17). 4-(Trifluoromethyl)-1,1 -biphenyl (3g). 11 Yield 81%; White solid; R f 0.70 (hexane); m.p. 96-97 C (hexane); IR (KBr) υ (cm -1 ) 3431, 3083, 2921, 2850, 2359, 1959, 1925, 1614, 1570, 1490, 1406, 1343, 1162, 1113, 1074, 843, 767, 728; δ H 7.69 (s, 4H), 7.60-7.58 (m, 2H), 7.49-7.38 (m, 3H); δ C 144.7, 139.8, 129.0 (q, J = 32 Hz), 128.2, 127.4, 127.3, 125.72, 125.68 (q, J = 3.6 Hz), 123 (q, J = 272 Hz); MS (m/z,%) 223 (M + +1, 15), 222 (M +, 100), 203 (10), 202 (12), 153 (17), 152 (29). 12

2-(Trifluoromethyl)-1,1 -biphenyl (3h). 12 Yield 78%; White solid; R f 0.70 (hexane); m.p. 15 C (hexane); IR (KBr) υ (cm -1 ) 3065, 2926, 1483, 1316, 1171, 1072, 768, 654; δ H 7.74 (d, J = 7.8 Hz, 1H), 7.61-7.52 (m, 1H), 7.48-7.31 (m, 7H); δ C 141.4, 139.8, 132.0, 131.2, 128.9, 128.7 (q, J = 32.6 Hz), 127.7, 127.6, 127.3, 127.1, 126.1(q, J = 10.6 Hz), 126.04, 125.97, 125.91 (q, J = 272 Hz); MS (m/z,%) 223 (M + +1, 18), 222 (M +, 100), 203 (15), 202 (14), 153 (21), 152 (35). 2,6-Dimethylbiphenyl (3i). 7 Yield 53%; Colorless oil; R f 0.74 (hexane); IR (neat) υ (cm - 1 ) 3054, 3013, 2948, 2915, 2842, 1460, 1439, 1374, 1010, 766, 705; δ H 7.52-7.38 (m, 3H), 7.28-7.16 (m, 5H), 2.10 (s, 6H); δ C 141.9, 141.4, 136.1, 129.1, 128.4, 127.3, 127.2, 127.0, 20.9; MS (m/z, %): 183 (M + +1, 14), 182 (M +, 92), 168 (14), 167 (100), 166 (29), 165 (51), 152 (22). 12. References 1. J. M. Matthews, PTC Int. Appl. WO 2010/080397 A1. 2. Quasdorf, K. W., Riener, M., Petrova, K. V., Garg, N. K. J. Am. Chem. Soc. 2009, 131, 17748. 3. Zhao, Y.-L., Li, Y., Li, Y., Gao, L.-X., Han, F.-S. Chem. Eur. J. 2010, 16, 4991. 4. Albaneze-Walker, J., Raju, R., Vance, J. A., Goodman, A. J., Reeder, M. R., Liao, J., Maust, M. T., Irish, P. A., Espino, P., Andrews, D. R. Org. Lett. 2009, 11, 1463. 13

5. Shirbin, S.J., Boughton, B. A., Zammit, S. C., Zanatta, S. D., Marcuccio, S. M., Hutton, C. A., Williams, S. J. Tetrahedron Lett. 2010, 51, 2971. 6. Molander, G. A., Beaumard, F. Org. Lett. 2010, 12, 42022. 7. Ren, G., Cui, X., Wu, Y. Eur. J. Org. Chem. 2010, 2372. 8. Denmark, S. E., Smith, R. C., Chang, W.-T. T., Muhuhi, J. M. J. Am. Chem. Soc. 2009, 131, 3104. 9. Martins, D. L., Alvarez, H. M., Aguiar, L. C. S. Tetrahedron Lett. 2010, 51, 6814. 10. So, C. M., Lau, C. P., Chan, A. S. C., Kwong, F. Y. J. Org. Chem. 2008, 73, 7731. 11. Ackermann, L., Potukuchi, H. K., Althammer, A., Born, R., Mayer, P. Org. Lett. 2010, 12, 1004. 12. Tu, T., Malineni, J., Bao, X., Dötz, K. H. Adv. Synth. Catal. 2009, 351, 1029. 14

15 9.01 1.08 1.10 2.21 1.07 0.95 1.00 1.595 7.309 7.311 7.328 7.330 7.439 7.459 7.478 7.485 7.489 7.502 7.507 7.513 7.520 7.526 7.531 7.533 7.538 7.551 7.555 7.726 7.747 7.855 7.860 7.871 7.878 7.955 7.956 7.959 7.961 7.963 7.973 7.974 7.979 27.360 83.206 117.528 120.814 125.096 125.693 126.164 126.204 126.668 127.691 134.384 146.670 151.768

154.807 147.203 134.539 127.883 127.323 126.158 125.425 125.314 121.186 118.119 36.792 36.512 16

O O N O P O N O O (2ac) Naphthalen-2-yl bis(2-oxooxazolidin-3-yl)phosphinate 17

146.065 134.786 127.891 127.093 126.713 126.603 125.325 121.430 117.723 38.855 1.00 1.01 1.01 3.08 1.02 6.04 8.186 8.184 8.165 8.163 7.876 7.857 7.767 7.747 7.590 7.587 7.573 7.570 7.566 7.549 7.531 7.529 7.512 7.509 7.466 7.447 7.427 3.048 18

145.231 137.425 134.766 131.302 128.666 128.010 127.645 127.366 126.335 125.033 120.366 118.396 117.776 4.12 2.11 1.03 1.00 0.99 1.00 7.907 7.896 7.888 7.882 7.865 7.836 7.819 7.801 7.786 7.776 7.584 7.563 7.550 7.538 7.516 7.432 7.406 7.379 7.303 7.113 7.006 6.981 19

148.873 137.427 131.249 130.232 128.556 121.218 118.230 1.00 3.02 1.08 0.99 2.01 7.724 7.386 7.374 7.361 7.352 7.338 7.304 7.299 7.274 7.165 6.943 6.931 6.926 6.918 6.910 20

21

22

200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 23

1.00 1.02 1.01 1.00 1.00 1.10 0.98 7.924 7.729 7.710 7.650 7.646 7.630 7.610 7.504 7.502 7.485 7.483 7.466 7.464 7.355 7.351 7.348 7.279 7.260 7.239 7.187 7.185 7.183 24

147.625 136.907 131.404 131.101 129.661 127.771 118.401 16.072 1.08 1.00 4.55 6.00 7.900 7.351 7.347 7.344 7.184 7.182 7.181 7.149 7.133 7.128 7.112 7.069 7.049 2.067 25

140.743 140.244 133.772 131.597 130.061 128.241 127.610 127.216 126.907 126.005 125.745 125.362 29.691 3.00 9.00 7.915 7.894 7.872 7.852 7.545 7.527 7.507 7.502 7.492 7.474 7.470 7.459 7.447 7.443 7.436 7.433 7.427 7.422 7.419 7.409 7.406 26

27 3.00 2.00 4.00 2.05 3.02 2.445 7.212 7.281 7.282 7.301 7.378 7.394 7.397 7.404 7.407 7.411 7.424 7.428 7.450 7.453 7.470 7.473 7.482 7.487 7.490 7.500 7.502 7.520 7.821 7.841 7.874 7.894 7.908 7.929 21.215 125.374 125.681 125.893 126.094 126.861 127.418 128.229 128.952 129.414 129.940 131.741 133.828 136.882 137.833 140.256

158.944 139.907 133.838 131.099 128.239 127.314 126.889 126.060 125.897 125.679 125.385 113.712 55.353 1.99 1.01 6.11 2.00 3.00 7.933 7.909 7.887 7.845 7.825 7.436 7.419 7.414 7.043 7.038 7.026 7.021 3.894 28

1.92 1.00 1.97 2.02 1.92 1.01 0.94 8.069 8.047 8.040 8.019 7.994 7.973 7.895 7.874 7.714 7.693 7.673 7.665 7.662 7.656 7.653 7.648 7.645 7.642 7.635 7.628 7.625 7.595 7.592 7.578 7.574 7.571 7.557 7.554 7.530 7.527 7.512 7.509 29

141.118 138.314 136.989 129.449 128.682 126.945 21.090 2.09 2.01 2.10 1.08 2.15 3.00 7.592 7.587 7.564 7.562 7.506 7.479 7.445 7.439 7.421 7.395 7.340 7.323 7.316 7.292 7.259 7.231 2.391 30

141.423 141.222 138.230 128.864 128.733 128.607 127.229 127.158 127.051 125.083 21.404 2.00 3.07 2.00 2.64 7.617 7.612 7.605 7.592 7.587 7.564 7.561 7.553 7.475 7.472 7.466 7.448 7.422 7.417 7.401 7.396 7.389 7.379 7.374 7.370 7.357 7.349 7.330 7.325 7.301 7.259 7.212 2.384 31

32

141.380 139.818 131.999 131.246 128.911 128.733 127.709 127.578 127.287 127.147 126.115 126.045 125.973 125.906 0.99 1.24 7.00 7.753 7.727 7.611 7.606 7.582 7.579 7.575 7.571 7.548 7.523 7.478 7.477 7.462 7.452 7.438 7.434 7.430 7.427 7.418 7.412 7.405 7.401 7.390 7.382 7.370 7.366 7.359 7.354 7.339 7.325 7.314 33

141.845 141.079 136.019 129.001 128.380 127.247 126.988 126.572 20.807 2.06 1.07 5.08 6.00 7.503 7.500 7.485 7.470 7.466 7.418 7.415 7.412 7.402 7.396 7.391 7.381 7.378 7.375 7.234 7.226 7.222 7.217 7.212 7.205 7.202 7.183 7.166 7.163 2.102 34