Supporting Information

Transcription

1 Supporting Information NiCl 2 (PMe 3 ) 2 -catalyzed Borylation of Aryl Chlorides Tetsuya Yamamoto, Tomoyuki Morita, Jun Takagi and Tetsu Yamakawa Sagami Chemical Research Institute, Hayakawa, Ayase, Kanagawa , Japan Table of Contents General Remarks S1 Experimental for the Borylation of Aryl Halides. S2-S3 Characterization Data of the Products: 2a-s S3-S8 References...S9 Copies of 1 H, 13 C, 11 B and 19 F NMR charts: 2a-s S10-S69

2 General Remarks All reactions were carried out under an Ar atmosphere. 1 H, 13 C, 19 F and 11 B NMR spectra were recorded on a Brucker AVANCE III 400 spectrometer ( MHz) at ambient temperature. The chemical shifts of 19 F and 11 B were referenced to the resonance frequency (0.0 ppm), 19 F MHz and 11 B MHz, with a negative sign indicating an upfield shift. GC-MS was run on a Shimadzu GC-MS QP2010 mass spectrometer. High-resolution mass spectra were taken with a JEOL MStaion JMS-700. IR spectra were recorded on a HORIBA FT-720. Characteristic IR absorptions are reported in cm -1. Melting points were recorded on a METTLER TOLEDO MP-70. The GC yields were determined by using tridecane as an internal standard on a Shimadzu GC-14B instrument equipped with an FID detector and a capillary column (HR-1, Shinwa, 50 m 0.25 mm, 0.25 µm i.d.). Dehydrated toluene, dehydrated THF, dehydrated 1,4-dioxane, EtOH, NiCl 2 (PMe 3 ) 2, NiCl 2 (PPh 3 ) 2, NiCl 2 (dppe), NiCl 2 (dppf), NiCl 2 6H 2 O, 1,2-dimethylphosphinoethane (dmpe), 1,1-diphenylphosphinomethane (dppm), 1,3-diphenylphosphinopropane (dppp), 1,4-diphenylphosphinobutane (dppb), 1,1 -diphenylphosphinoferrocene (dppf), bis(pinacolato)diboron, K 3 PO 4, K 2 CO 3, Rb 2 CO 3, AcOK, t-buok, CsF, NEt 3, methyl 4-chlorobenzoate (1a), 4-chloroacetophenone (1b), 4-chlorobenzophenone (1c), 4-chlorobenzamide (1d), 3-chloroacetoanilide (1e), 4-(4-chlorophenyl)morpholine (1f), 5-chloro-2-fluoroaniline (1g), 4-chlorobenzaldehyde diethyl acetal (1h), 4-chloro-α-methylstyrene (1k), 4-chloroanisole (1l), ethyl 2-chlorobenzoate (2m), 2-chloroaniline (1n), 2 -chloro-2,2-dimethylpropionanilide (1o), 2-chlorobenzotrifluoride (1p), 2-chloro-1,3-dimethylbenzene (1s), ethyl 2-bromobenzoate (3a), 2-bromoaniline (3b), 4-chlorophenylboronic acid, 3-chloro-4-fluorophenylboronic acid, 2-chlorophenylboronic acid, 1,8-diamino- naphthalene, chlorotrimethylsilane and 1-methylimidazole were obtained from commercial suppliers. 1-chloro-4-(4-chlorobutoxy)benzene (1j) and 2,2,2-trifluoroethanol were provided by Tosoh corporation and Tosoh F-Tech Inc., respectively. NiCl 2 (dppm), 1 NiCl 2 (dmpe), 2 NiCl 2 (dppp), 3 NiCl 2 (dppb), 4 PhOK 5 and (2,2,2-trifluoroethoxy)trimethyl silane (TMSOCH 2 CF 3 ) 6 were prepared according to the literature procedures. 4-chloro-1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl)benzene (1i), 3-chloro-4-fluoro-1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl)benzene (1q), 2-chloro-1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl)benzene (1r) were prepared from 4-chlorophenylboronic acid, 3-chloro-4-fluorophenylboronic acid and 2-chlorophenylboronic acid with 1,8-diaminonaphthalene according to the reported procedure. 7 S1

3 Experimental for the Borylation of Aryl Halides Ni-catalyzed borylation of methyl 4-chlorobenzoate (Table 1 entries 1,2, 4-12 and Table 2 entries 1-7 ). A 10 ml test tube sealed with a rubber septum was charged with Ni complex ( mmol), dppf (0 or 0.05 mmol), methyl 4-chlorobenzoate (85.3 mg, 0.5 mmol), bis(pinacolato)diboron (152 mg, 0.6 mmol) and a base (1.0 mmol). Then the test tube was evacuated and backfilled with argon. This sequence was carried out five times. After toluene (1.0 ml) was added via syringe, the rubber septum was replaced with a Teflon liner screw cap. The resulting mixture was placed into an oil bath preheated at 100 C. After the reaction mixture was stirred for 12 h and cooled to room temperature ethyl acetate (8 ml), a saturated aqueous solution of NH 4 Cl (1 ml) and tridecane (20 µl) as an internal standard were added. An aliquot of the organic layer of the reaction mixture was subjected to the quantitative analysis by GC. NiCl 2 (dppp)/dppf-catalyzed borylation of methyl 4-chlorobenzoate using NEt 3 (Table 1 entry 3 ). A 10 ml test tube sealed with a rubber septum was charged with NiCl 2 (dppp) (13.6 mg, mmol), dppf (27.7 mg, 0.05 mmol), methyl 4-chlorobenzoate (85.3 mg, 0.5 mmol) and bis(pinacolato)diboron (152 mg, 0.6 mmol). Then the test tube was evacuated and backfilled with argon. This sequence was carried out five times. After toluene (1.0 ml) and NEt 3 (152 mg, 1.5 mmol) was added via syringe, the rubber septum was replaced with a Teflon liner screw cap. The resulting mixture was placed into an oil bath preheated at 100 C. This reaction temperature is higher than the boiling point of NEt 3. After the reaction mixture was stirred for 12 h and cooled to room temperature, ethyl acetate (8 ml), a saturated aqueous solution of NH 4 Cl (1 ml) and tridecane (20 µl) as an internal standard were added. An aliquot of the organic layer of the reaction mixture was subjected to the quantitative analysis by GC. General procedure A: NiCl 2 (PMe 3 ) 2 -catalyzed borylation of solid aryl chlorides (Table 2 entries 8-13, Table 3 entries 2-5, Table 4 entries 5, 7 and 8). A 10 ml test tube sealed with a rubber septum was charged with NiCl 2 (PMe 3 ) 2 ( mmol), an aryl chloride (0.5 mmol), bis(pinacolato)diboron ( mmol) and a base (1.0 mmol). Then the test tube was evacuated and backfilled with argon. This sequence was carried out five times. After a solvent (toluene, THF or 1,4-dioxane, ml) and an additive (H 2 O, EtOH, CF 3 CH 2 OH or TMSOCH 2 CF 3, mmol) was added via syringe, the rubber septum was replaced with a Teflon liner screw cap. The resulting mixture was placed into an oil bath preheated at C. This reaction temperature is higher than the boiling point of THF, EtOH and CF 3 CH 2 OH. After the reaction mixture was stirred for 3-12 h and cooled to room temperature, ethyl acetate (8 ml), a saturated aqueous solution of NH 4 Cl (1 ml) and tridecane (20 µl) as an internal standard were added. An aliquot of the organic layer of the reaction mixture was subjected to the quantitative analysis by GC. The desired product was extracted into ethyl acetate (2 8.0 ml). The organic layers were combined and concentrated in vacuo. The obtained crude residue was purified by passing it through a silica gel column with a hexane/chloroform /ethyl acetate eluent. General procedure B: NiCl 2 (PMe 3 ) 2 -catalyzed borylation of liquid aryl halides (Table 3 entries 1, 6, 7 and 9-11, Table 4 entries 1-4, 6 and 9). A 10 ml test tube sealed with a rubber septum was charged with NiCl 2 (PMe 3 ) 2 ( mmol), bis(pinacolato)diboron ( mmol) and CsF ( mmol). Then the test tube was evacuated and backfilled with argon. This sequence was carried out five times. After a solvent (toluene, THF or 1,4-dioxane, 0.5 S2

4 ml), an aryl halide (0.5 mmol) and TMSOCH 2 CF 3 ( mmol) was added via syringe, the rubber septum was replaced with a Teflon liner screw cap. The resulting mixture was placed into an oil bath preheated at C. This reaction temperature is higher than the boiling point of THF. After the reaction mixture was stirred for 1-12 h and cooled to room temperature, ethyl acetate (8 ml), a saturated aqueous solution of NH 4 Cl (1 ml) and tridecane (20 µl) as an internal standard were added. An aliquot of the organic layer of the reaction mixture was subjected to the quantitative analysis by GC. The product was extracted into ethyl acetate (2 8.0 ml). The organic layers were combined and concentrated in vacuo. The obtained crude residue was purified by passing it through a silica gel column with a hexane/chloroform /ethyl acetate eluent or bulb-to-bulb distillation. Characterization Data of the Products 2a 8 : methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (Table 2 entry 12) Following procedure A, a mixture of methyl 4-chlorobenzoate (84.9 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (1.4 mg, O O B O OMe mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 129 mg of the title compound (99 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 8.02 (d, 2H, J = 8.3 Hz), 7.87 (d, 2H, J = 8.3 Hz), 3.92 (s, 3H), 1.36 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 167.1, 134.6, 132.3, 128.6, 84.2, 52.1, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.6.; EI-MS: m/z b 8 : 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]ethanone (Table 3 entry 1) Following procedure B, a mixture of 4-chloroacetophenone (76.5 mg, 0.49 mmol), NiCl 2 (PMe 3 ) 2 (2.8 mg, 0.01 O O B mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 98.7 mg of the title compound (81 % yield) as a white O solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.93 (d, 2H, J = 8.4 Hz), 7.89 (d, 2H, J = 8.4 Hz), 2.62 (s, 3H), 1.36 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 198.4, 139.0, 134.9, 127.2, 84.2, 26.7, 24.8.; 11 B NMR (CDCl 3, 128 MHz) δ 30.5.; EI-MS: m/z c 9 : [4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl](phenyl)methanone (Table 3 entry 2) Following procedure A, a mixture of 4-chlorobenzophenone (108 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (1.4 mg, O B O O Ph mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 112 mg of the title compound (73 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.92 (d, 2H, J = 8.2 Hz), (m, 4H), 7.59 (t, 1H, J = 7.4 Hz), 7.48 (d, 2H, J = 7.4 Hz), 1.37 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 196.9, 139.8, 137.5, 134.5, 132.5, 130.1, 129.0, 128.3, 84.2, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.3.; EI-MS: m/z 308. S3

5 2d 10 : 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide (Table 3 entry 3) Following procedure A, a mixture of 4-chlorobenzamide (77.4 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (1.4 mg, O O B mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in 1,4-dioxane (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl O NH 2 acetate (4/1/0 to 4/1/1) eluent yielded 92.4 mg of the title compound (75 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.88 (d, 2H, J = 8.2 Hz), 7.80 (d, 2H, J = 8.2 Hz), 6.21 (brs, 2H), 1.36 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 169.5, 135.6, 135.0, 126.4, 84.2, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.7.; EI-MS: m/z e 11 : N-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]acetamide (Table 3 entry 4) Following procedure A, a mixture of 3-chloroacetoanilide (85.1 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (1.4 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in 1,4-dioxane (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (4/1/0 to 4/1/1) eluent yielded 122 mg of the title compound (93 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.87 (d, 1H, J = 7.6 Hz), 7.66 (s, 1H), 7.53 (d, 1H, J = 7.6 Hz), 7.49 (s, 1H), 7.33 (dd, 1H, J = 7.6, 7.6 Hz), 2.15 (s, 3H), 1.33 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 168.4, 137.4, 130.6, 128.6, 125.9, 123.2, 83.9, 24.9, 24.5.; 11 B NMR (CDCl 3, 128 MHz) δ 30.6.; EI-MS: m/z f 11 : 4-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]morpholine (Table 3 entry 5) Following procedure A, a mixture of 4-(4-Chlorophenyl)morpholine (98.4 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 O mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), O B N O and heated at 100 C for 12 h. Column chromatography with a hexane/ chloroform/ethyl acetate (4/1/0 to 4/1/1) eluent yielded 123 mg of the title compound (86 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.72 (d, 2H, J = 8.6 Hz), 6.87 (d, 2H, J = 8.6 Hz), 3.84 (t, 4H, J = 4.8 Hz), 3.21 (t, 4H, J = 4.8 Hz), 1.32 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 153.4, 136.2, 114.1, 83.4, 66.8, 48.4, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.8.; EI-MS: m/z g 11 : 2-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (Table 3 entry 6) Following procedure B, a mixture of 5-chloro-2-fluoroaniline (72.8 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, O B O yellow solid. NH 2 F mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (4/1/0 to 4/1/1) eluent yielded 95.7 mg of the title compound (81 % yield) as a pale mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.23 (dd, 1H, J = 1.6, 9.6 Hz), 7.16 (ddd, 1H, J = 1.6, 5.3, 8.0 Hz), 6.97 (dd, 1H, J = 8.0, 11.3 Hz), 3.68 (brs, 2H), 1.33 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ (d, 1C, J S4

6 = Hz), (d, 1C, J = 12.2 Hz), (d, 1C, J = 7.1 Hz), (d, 1C, J = 4.3 Hz), (d, 1C, J = 17.9 Hz), 83.8, 24.9; 19 F NMR (CDCl 3, 376 MHz) δ ; 11 B NMR (CDCl 3, 128 MHz) δ 30.7.; EI-MS: m/z h 12 : 2-[4-(diethoxymethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3 entry 7) Following procedure B, a mixture of 4-Chlorobenzaldehyde diethyl acetal (83.8 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 O B O (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ ethyl acetate (16/4/0 to 16/4/1) eluent yielded 93.4 mg of the title compound (72 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.76 (d, 2H, J = 8.2 Hz), 7.40 (d, 2H, J = 8.4 Hz), 1.33 (s, 12H), 1.32 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 154.5, 134.7, 124.7, 83.6, 34.9, 31.2, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 25.6.; EI-MS: m/z i 13 : 2,3-Dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (Table 3 entry 8) Following procedure A, a mixture of 4-chloro-1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl)benzene O O B B HN H N (139 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ ethyl acetate (4/1/0 to 4/1/1) eluent yielded 153 mg of the title compound (82% yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.87 (d, 2H, J = 8.2 Hz), 7.64 (d, 2H, J = 8.2 Hz), 7.13 (dd, 2H, J = 7.2, 8.2 Hz), 7.05 (dd, 2H, J = 0.8, 8.2 Hz), 6.41 (dd, 2H, J = 0.8, 7.2 Hz), 6.04 (brs, 2H), 1.36 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 141.0, 136.4, 134.5, 130.7, 127.6, 119.9, 117.9, 106.1, 84.0, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 29.0.; EI-MS: m/z j: 2-[4-(4-chlorobutoxy)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3 entry 9) Following procedure B, a mixture of 1-chloro-4-(4-chlorobutoxy)benzene (110 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 O O B Cl (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl O acetate (16/4/0 to 16/4/1) eluent yielded 122 mg of the title compound (78 % yield) as a white solid. R f = 0.51 (hexane/chloroform/ethyl acetate = 16/4/1); mp C; IR (neat) 2978, 2931, 2871, 1604, 1568, 1396, 1358, 1319, 1275, 1142, 1090, 1053, 860, 831, 737, 652.; 1 H NMR (CDCl 3, 400 MHz) δ 7.74 (d, 2H, J = 8.7 Hz), 6.88 (d, 2H, J = 8.7 Hz), 4.02 (t, 2H, J = 5.8 Hz), 3.62 (t, 2H, J = 6.2 Hz), (m, 4H), 1.33 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 161.5, 136.5, 113.8, 83.5, 66.8, 44.7, 29.3, 26.6, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.7.; HRMS (EI) m/z [M] + calcd for C 16 H 24 BClO ; found S5

7 2k: 4,4,5,5-tetramethyl-2-[4-(prop-1-en-2-yl)phenyl]-1,3,2-dioxaborolane (Table 3 entry 10) Following procedure B, a mixture of 4-chloro-α-methylstyrene (74.7 mg, 0.49 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, O O B mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 94.1 mg of the title compound (79 % yield) as a white solid. R f = 0.78 (hexane/chloroform/ethyl acetate = 4/1/1); mp C; IR (neat) 3087, 2976, 2929, 1610, 1550, 1520, 1398, 1358, 1321, 1265, 1144, 1120, 1084, 1018, 964, 894, 858, 843, 831, 694, 653.; 1 H NMR (CDCl 3, 400 MHz) δ 7.77 (d, 2H, J = 8.3 Hz), 7.46 (d, 2H, J = 8.3 Hz), 5.41 (dd, 1H, J = 0.8, 1.5 Hz), 5.11 (dd, 1H, J = 1.5, 1.5 Hz), 2.15 (dd, 3H, J = 0.8, 1.5 Hz), 1.33 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 144.0, 143.3, 134.8, 124.8, 113.2, 83.7, 24.9, 21.7.; 11 B NMR (CDCl 3, 128 MHz) δ 30.7.; HRMS (EI) m/z [M] + calcd for C 15 H 21 BO ; found l 8 : 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3 entry 11) Following procedure B, a mixture of 4-chloroanisole (70.6 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (7.0 mg, mmol), O O B bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 2 h. Column chromatography with a hexane/chloroform/ethyl acetate OMe (16/4/0 to 16/4/1) eluent yielded 107 mg of the title compound (93 % yield) as a colorless liquid. 1 H NMR (CDCl 3, 400 MHz) δ 7.75 (d, 2H, J = 8.6 Hz), 6.89 (d, 2H, J = 8.6 Hz), 3.81 (s, 3H), 1.33 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 162.1, 136.5, 113.3, 83.5, 55.0, 24.8.; 11 B NMR (CDCl 3, 128 MHz) δ 30.8.; EI-MS: m/z m 14 : ethyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (Table 4 entry 1) Following procedure B, a mixture of ethyl 2-chlorobenzoate (91.4 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (7.0 mg, O O O B OEt mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 2 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 107 mg of the title compound (78 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.93 (ddd, 1H, J = 0.8, 0.8, 7.8 Hz), (m, 2H), 7.40 (ddd, 1H, J = 3.4, 5.3, 7.8 Hz), 4.38 (q, 2H, J = 7.2 Hz), 1.42 (s, 12H), 1.38 (t, 3H, J = 7.2 Hz); 13 C NMR (CDCl 3, 100 MHz) δ 168.1, 133.9, 132.1, 131.7, 128.8, 128.5, 84.0, 61.2, 24.9, 14.3.; 11 B NMR (CDCl 3, 128 MHz) δ 31.6.; EI-MS: m/z m 14 (Table 4 entry 3) Following procedure B, a mixture of ethyl 2-bromobenzoate (115 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (7.0 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in toluene (0.5 ml), and heated at 100 C for 1 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 112 mg of the title compound (81 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.93 (ddd, 1H, J = 0.8, 0.8, 7.8 Hz), (m, 2H), 7.40 S6

8 (ddd, 1H, J = 3.4, 5.3, 7.8 Hz), 4.38 (q, 2H, J = 7.2 Hz), 1.42 (s, 12H), 1.38 (t, 3H, J = 7.2 Hz); 13 C NMR (CDCl 3, 100 MHz) δ 168.1, 133.9, 132.1, 131.7, 128.8, 128.5, 84.0, 61.2, 24.9, 14.3.; 11 B NMR (CDCl 3, 128 MHz) δ 31.6.; EI-MS: m/z n 15 : 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (Table 4 entry 2) Following procedure B, a mixture of 2-chloroaniline (63.3 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 O NH 2 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Crude B O residue was purified by bulb-to-bulb distillation at 125 C / 1.5 mmhg, giving 87.0 mg of the title compound (80 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.61 (dd, 1H, J = 7.3 Hz), 7.21 (ddd, 1H, J = 1.7, 7.3, 8.2 Hz), 6.67 (ddd, 1H, J = 1.0, 7.3, 7.3 Hz), 6.59 (d, 1H, J = 8.2 Hz), 4.71 (brs, 2H), 1.34 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 153.6, 136.8, 132.7, 116.9, 114.8, 83.5, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.8.; EI-MS: m/z n 15 (Table 4 entry 4) Following procedure B, a mixture of 2-bromoaniline (84.9 mg, 0.49 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in toluene (0.5 ml), and heated at 100 C for 1 h. Crude residue was purified by bulb-to-bulb distillation at 125 C / 1.5 mmhg, giving 90.9 mg of the title compound (84 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.61 (dd, 1H, J = 7.3 Hz), 7.21 (ddd, 1H, J = 1.7, 7.3, 8.2 Hz), 6.67 (ddd, 1H, J = 1.0, 7.3, 7.3 Hz), 6.59 (d, 1H, J = 8.2 Hz), 4.71 (brs, 2H), 1.34 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 153.6, 136.8, 132.7, 116.9, 114.8, 83.5, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 30.8.; EI-MS: m/z o 11 : 2,2-dimethyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]propionamide (Table 4 entry 5) Following procedure A, a mixture of 2 -chloro-2,2-dimethylpropionanilide (106 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in 1,4-dioxane (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/ chloroform/ethyl acetate (4/1/0 to 4/1/1) eluent yielded 129 mg of the title compound (85 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 9.53 (brs, 1H), 8.56 (d, 1H, J = 7.4 Hz), 7.77 (d, 1H, J = 7.4 Hz), 7.45 (dd, 1H, J = 7.4, 7.4 Hz), 7.05 (dd, 1H, J = 7.4, 7.4 Hz), 1.38 (s, 12H), 1.33 (s, 9H); 13 C NMR (CDCl 3, 100 MHz) δ 177.1, 145.2, 136.3, 132.9, 122.6, 119.2, 84.3, 40.1, 27.6, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 28.5.; EI-MS: m/z p 16 : 4,4,5,5-tetramethyl-2-[2-(trifluoromethyl)phenyl]-1,3,2-dioxaborolane (Table 4 entry 7) Following procedure B, a mixture of 2-chlorobenzotrifluoride (89.6 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (2.8 mg, mmol), bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/chloroform/ethyl acetate (16/4/0 to 16/4/1) eluent yielded 119 mg of the title compound (88 % yield) as a colorless liquid. 1 H NMR (CDCl 3, 400 MHz) δ (m, 2H), (m, 2H), 1.37 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 134.7, (q, 1C, J = 31.2 Hz), 130.7, 129.9, (q, 1C, J = 5.0 Hz), (d, 1C, J = Hz), S7

9 84.46, 24.6; 19 F NMR (CDCl 3, 376 MHz) δ ; 11 B NMR (CDCl 3, 128 MHz) δ 31.2.; EI-MS: m/z q: 1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl)-2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)benzen (Table 4 entry 8) Following procedure A, a mixture of 3-chloro-4-fluoro-1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl) benzene (149 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (4.2 mg, mmol), O B O F HN B NH bis(pinacolato)diboron (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 100 C for 12 h. Column chromatography with a hexane/ chloroform/ethyl acetate (4/1/0 to 4/1/1) eluent yielded 165 mg of the title compound (85 % yield) as a white solid. R f = 0.32 (hexane/chloroform/ethyl acetate = 4/1/1); mp C; IR (neat) 3413, 3373, 2987, 1599, 1518, 1487, 1392, 1343, 1214, 1133, 1072, 964, 850, 822, 775, 746, 644.; 1 H NMR (CDCl 3, 400 MHz) δ 8.02 (dd, 1H, J = 2.0, 6.2 Hz), 7.72 (ddd, 1H, J = 2.0, 5.8, 7.8 Hz), (m, 5H), 6.43 (dd, 2H, J = 0.8, 7.2 Hz), 6.04 (brs, 2H), 1.40 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ (d, 1C, J = Hz), 141.0, (d, 1C, J = 8.0 Hz), (d, 1C, J = 8.8 Hz), 136.4, 127.6, 119.8, 117.9, (d, 1C, J = 22.9 Hz), 106.1, 84.1, 24.9; 19 F NMR (CDCl 3, 376 MHz) δ ; 11 B NMR (CDCl 3, 128 MHz) δ 29.8.; HRMS (EI) m/z [M] + calcd for C 22 H 23 B 2 FN 2 O ; found r 13 : 2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzen (Table 4 entry 9) Following procedure A, a mixture of 2-chloro-1-(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaborinyl)benzene (139 mg, 0.50 mmol), NiCl 2 (PMe 3 ) 2 (7.0 mg, mmol), bis(pinacolato)diboron O B O HN B NH (140 mg, 0.55 mmol), CsF (152 mg, 1.0 mmol) and TMSOCH 2 CF 3 (180 mg, 1.05 mmol) was dissolved in THF (0.5 ml), and heated at 120 C for 3 h. Column chromatography with a hexane/chloroform/ ethyl acetate (4/1/0 to 4/1/1) eluent yielded 158 mg of the title compound (86 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.82 (dd, 1H, J = 1.0, 7.3 Hz), 7.63 (dd, 1H, J = 1.0, 7.3 Hz), (m, 2H), 7.12 (dd, 2H, J = 7.3, 8.3 Hz), 7.02 (dd, 2H, J = 0.8, 8.3 Hz), 6.39 (brs, 2H), 6.33 (dd, 2H, J = 0.8, 7.3 Hz), 1.34 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 141.7, 136.5, 135.1, 132.3, 130.2, 128.6, 127.7, 119.9, 117.3, 105.6, 84.3, 24.9.; 11 B NMR (CDCl 3, 128 MHz) δ 31.4.; EI-MS: m/z s 17 : 4,4,5,5-tetramethyl-2-(2,6-dimethylphenyl)-1,3,2-dioxaborolane (Table 4 entry 10) Following procedure B, a mixture of 2-chloro-1,3-dimethylbenzene (70.4 mg, 0.5 mmol), NiCl 2 (PMe 3 ) 2 (14.0 mg, O B O 0.05 mmol), bis(pinacolato)diboron (252 mg, 1.0 mmol), CsF (225 mg, 1.5 mmol), and TMSOCH 2 CF 3 (300 mg, 1.74 mmol) was dissolved in 1,4-dioxane, and heated at 135 C for 12 h. Column chromatography with a hexane/chloroform /ethyl acetate (27/3/0 to 27/3/1) eluent yielded 105 mg of the title compound (90 % yield) as a white solid. mp C; 1 H NMR (CDCl 3, 400 MHz) δ 7.12 (t, 1H, J = 7.6 Hz), 6.93 (d, 2H, J = 7.6 Hz), 2.39 (s, 6H), 1.38 (s, 12H); 13 C NMR (CDCl 3, 100 MHz) δ 141.8, 129.2, 126.4, 83.7, 25.0, 22.2.; 11 B NMR (CDCl 3, 128 MHz) δ 32.1.; EI-MS: m/z 232. S8

10 References (1) Zayed, M. A.; Arifien, A. E-S. A.; Hassan, F. S. M. J. Thermal Anal, 1999, 55, (2) Booth, G.; Chartt, J. J. Chem. Soc. 1965, (3) Van Hecke, G. R.; Horrocks, W. D. Inorg. Chem. 1966, 5, (4) Sacconi, L.; Gelsomini, J. Inorg. Chem. 1968, 7, 291. (5) Kornblum, N.; Lurie, A. P. J. Am. Chem. Soc. 1959, 81, (6) Lee, B.; Kim, J.-H.; Lee, H.; Ahn, B.-S.; Cheong, M.; Kim, H.-S.; Kim, H. J. Fluor. Chem. 2007, 128, 110. (7) Noguchi, H.; Hojo, K.; Suginome, M. J. Am. Chem. Soc. 2007, 129, 758. (8) Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, (9) Billingsley, K. L.; Buchwald, S. L. J. Org. Chem. 2008, 73, (10) Brown, S. D.; Armstrong, R. W. J. Am. Chem. Soc. 1996, 118, (11) Identity of products was confirmed by comparison with the spectroscopic data of the commercial product. (12) Kim, S. K.,; Park, J. W.; Oh, S. Y. Mol. Cryst. Liq. Cryst. 2007, 471, 89. (13) Noguchi, H.; Shioda, T.; Chou, C.-M.; Suginome, M. Org. Lett. 2008, 10, 377. (14) Tsukamoto, H.; Kondo, Y. Org. Lett. 2007, 9, (15) Baudoin, O.; Guenard, D.; Gueritte, F. J. Org. Chem. 2000, 65, (16) Demory, E.; Blandin, V.; Einhorn J.; Chavant, P. Y. Org. Process Res. Dev. 2011, 15, 710. (17) Billingsley, K. L.; Barder, T. E.; Buchwald, S. L. Angew. Chem., Int. Ed. 2007, 46, S9

11 Copies of 1 H, 13 C, 11 B and 19 F NMR the Compounds 1 H NMR of Compound 2a S10

12 13 C NMR of Compound 2a S11

13 11 B NMR of Compound 2a S12

14 1 H NMR of Compound 2b S13

15 13 C NMR of Compound 2b S14

16 11 B NMR of Compound 2b S15

17 1 H NMR of Compound 2c S16

18 13 C NMR of Compound 2c S17

19 11 B NMR of Compound 2c S18

20 1 H NMR of Compound 2d S19

21 13 C NMR of Compound 2d S20

22 11 B NMR of Compound 2d S21

23 1 H NMR of Compound 2e S22

24 13 C NMR of Compound 2e S23

25 11 B NMR of Compound 2e S24

26 1 H NMR of Compound 2f S25

27 13 C NMR of Compound 2f S26

28 11 B NMR of Compound 2f S27

29 1 H NMR of Compound 2g S28

30 13 C NMR of Compound 2g S29

31 19 F NMR of Compound 2g S30

32 11 B NMR of Compound 2g S31

33 1 H NMR of Compound 2h S32

34 13 C NMR of Compound 2h S33

35 11 B NMR of Compound 2h S34

36 1 H NMR of Compound 2i S35

37 13 C NMR of Compound 2i S36

38 11 B NMR of Compound 2i S37

39 1 H NMR of Compound 2j S38

40 13 C NMR of Compound 2j S39

41 11 B NMR of Compound 2j S40

42 1 H NMR of Compound 2k S41

43 13 C NMR of Compound 2k S42

44 11 B NMR of Compound 2k S43

45 1 H NMR of Compound 2l S44

46 13 C NMR of Compound 2l S45

47 11 B NMR of Compound 2l S46

48 1 H NMR of Compound 2m S47

49 13 C NMR of Compound 2m S48

50 11 B NMR of Compound 2m S49

51 1 H NMR of Compound 2n S50

52 13 C NMR of Compound 2n S51

53 11 B NMR of Compound 2n S52

54 1 H NMR of Compound 2o S53

55 13 C NMR of Compound 2o S54

56 11 B NMR of Compound 2o S55

57 1 H NMR of Compound 2p S56

58 13 C NMR of Compound 2p S57

59 19 F NMR of Compound 2p S58

60 11 B NMR of Compound 2p S59

61 1 H NMR of Compound 2q S60

62 13 C NMR of Compound 2q S61

63 19 F NMR of Compound 2q S62

64 11 B NMR of Compound 2q S63

65 1 H NMR of Compound 2r S64

66 13 C NMR of Compound 2r S65

67 11 B NMR of Compound 2r S66

68 1 H NMR of Compound 2s S67

69 13 C NMR of Compound 2s S68

70 11 B NMR of Compound 2s S69