*3.4. Analytical data of products 12–25*

#### *3-(Phenylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-benzotrifluoride (12)*

From Sonogashira coupling of borylated aryl bromide: the general procedure A was applied to the borylated version of 3-bromobenzotrifluoride (**9**, 351 mg, 1.0 mmol, 1 equiv) with phenyl acetylene (121 μL, 112 mg, 1.10 mmol, 1.1 equiv) as the coupling partner for 10 h. The crude mixture was concentrated and passed through a plug of silica gel (CH2Cl2 as eluent) to furnish the desired product as orange yellow oil, which solidified on standing (280 mg, 75% yield, mp 74–75 ◦C).

From one-pot CHB/Sonogashira coupling: the general procedure B was applied to 3-bromobenzotrifluoride (279 μL, 450 mg, 2.0 mmol, 1 equiv). The borylation step was carried out with HBpin (436 μL, 384 mg, 3.00 mmol, 1.50 equiv) for 3 h. The Sonogashira coupling step was carried out with phenyl acetylene (242 μL, 225 mg, 2.20 mmol, 1.1 equiv) for 5 h. Gradient column chromatography (pentane:dichloromethane 4:1 → pentane:dichloromethane 1:1) furnished the desired product as orange yellow oil, which solidified on standing (473 mg, 64% yield, mp 74–75 ◦C).

1H NMR (CDCl3, 300 MHz): δ 8.15 (m, 1 H), 8.00 (m, 1.0 Hz, 1 H), 7.86 (m, 1 H), 7.58–7.49 (m, 2 H), 7.42–7.30 (m, 3 H), 1.37 (s, 12 H, 4 CH3 of Bpin). 13C-NMR {1H} (CDCl3, 125 MHz): δ 141.2 (CH), 131.8 (2 CH), 130.8 (q, <sup>3</sup>*J*C–F = 3.8 Hz, CH), 130.7 (q, <sup>3</sup>*J*C–F = 3.8 Hz, CH), 130.6 (q, <sup>2</sup>*J*C–F = 32.5 Hz, C), 128.8 (CH), 128.5 (2 CH), 124.1 (q, <sup>1</sup>*J*C–F = 273 Hz, CF3), 124.0 (C), 122.9 (C), 91.2 (C), 88.0 (C), 84.6 (2 C), 24.9 (4 CH3 of Bpin); 11B-NMR (CDCl3, 96 MHz): <sup>δ</sup> 30.6; 19F-NMR (CDCl3, 282 MHz) <sup>δ</sup> <sup>−</sup>63.0; FT-IR (neat) Іmax: 2980, 1601, 1493, 1369, 1306, 1277, 1169, 1130, 966, 898, 871, 847, 756, 704, 688 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 372 (100), 357 (10), 286 (18), 272 (12); HRMS (FAB): *m*/*z* 372.1510 [(M+); Calcd for C21H20BF3O2: 372.1508].

#### *3-(Trimethylsilylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-toluene (13)*

From Sonogashira coupling of borylated aryl bromide: the general procedure A was applied to the borylated version of 3-bromotoluene (**10**, 297 mg, 1.0 mmol, 1 equiv) with trimethylsilyl acetylene (156 μL, 108 mg, 1.10 mmol, 1.1 equiv) as the coupling partner for 4 h. Column chromatography (pentane/ether 9:1, R*<sup>f</sup>* 0.8) furnished the desired product as yellow oil (194 mg, 62% yield).

From one-pot CHB/Sonogashira coupling: the general procedure B was applied to 3-bromotoluene (122 μL, 171 mg, 1.0 mmol, 1 equiv). The borylation step was carried out with HBpin (218 μL, 192 mg, 1.50 mmol, 1.50 equiv) for 12 h. The Sonogashira coupling step was carried out with trimethylsilyl acetylene (156 μL, 108 mg, 1.10 mmol, 1.1 equiv) for 4 h. Column chromatography (pentane/ether 9:1, R*<sup>f</sup>* 0.8) furnished the desired product as yellow oil (204 mg, 65% yield).

1H NMR (CDCl3, 500 MHz): δ 7.74 (m, 1 H), 7.56 (m, 1 H), 7.38 (m, 1 H), 2.31 (m, 3 H), 1.34 (br s, 12 H, 4 CH3 of Bpin), 0.22 (s, 9 H, 3 CH3 of TMS); 13C-NMR {1H} (CDCl3, 125 MHz): δ 137.3 (C), 135.7 (CH), 135.5 (CH), 135.2 (CH), 122.7 (C), 105.4 (C), 93.8 (C), 84.1 (2 C), 25.0 (4 CH3 of Bpin), 21.1 (CH3), 0.2 (3 CH3 of TMS); 11B-NMR (CDCl3, 160 MHz): δ 30.2; FT-IR (neat) Іmax: 2978, 2154, 1591, 1383, 1365, 1248, 1145, 966, 848, 760, 706 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 314 (15), 299 (100), 199 (11); HRMS (FAB): *m*/*z* 314.1875 [(M+); Calcd for C18H27BO2Si: 314.1873].

#### *3-(Trimethylsilylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-chlorobenzene (14).*

From Sonogashira coupling of borylated aryl bromide: the general procedure A was applied to the borylated version of 3-bromochlorobenzene (**11**, 10 g, 31.5 mmol, 1 equiv) with 1,4-diazabicyclo[2.2.2]octane [DABCO] (3.54 g, 31.5 mmol, 1 equiv), allylpalladium chloride dimer (288 mg, 0.788 mmol, 2.5 mol %), P*t-*Bu3 (638 mg, 3.15 mmol, 10 mol %), trimethylsilyl acetylene (4.5 mL, 3.09 g, 31.5 mmol, 1 equiv) and acetonitrile (100 mL) for 4 h. After completion, 100 mL of water was added to the reaction mixture. The reaction mixture was extracted with MTBE (50 mL × 3). The combined ether extractions were washed with water (50 mL), followed by brine (50 mL), dried over MgSO4 before being concentrated under reduced pressure on a rotary evaporator. Gradient column chromatography (hexanes/ dichloromethane 1:1 → hexanes/dichloromethane 0:1) furnished the desired product as yellow oil. If the oil is left to dry in air, it will dry to a waxy solid that can be scraped and dried under vacuum to a yellow powder (8 g, 76% yield).

From one-pot CHB/Sonogashira coupling: the general procedure B was applied to 3-bromochlorobenzene (118 μL, 191 mg, 1.0 mmol, 1 equiv). The borylation step was carried out with HBpin (218 μL, 192 mg, 1.50 mmol, 1.50 equiv) for 4 h. The Sonogashira coupling step was carried out with trimethylsilyl acetylene (184 μL, 128 mg, 1.30 mmol, 1.3 equiv) for 4 h. Gradient column chromatography (hexanes/ dichloromethane 1:1 → hexanes/dichloromethane 0:1) furnished the desired product as yellow oil (196 mg, 59% yield).

1H-NMR (CDCl3, 300 MHz): δ 7.78 (dd, *J* = 1.5, 1.0 Hz, 1 H), 7.70 (dd, *J* = 2.2, 1.0 Hz, 1 H), 7.52 (dd, *J* = 2.2, 1.5 Hz, 1 H), 1.34 (br s, 12 H, 4 CH3 of Bpin), 0.23 (s, 9 H, 3 CH3 of TMS); 13C NMR {1H} (CDCl3, 125 MHz): δ 136.5 (CH), 134.6 (CH), 134.2 (CH), 133.9 (C), 124.6 (C), 103.6 (C), 95.8 (C), 84.5 (2 C), 25.0 (4 CH3 of Bpin), 0.0 (3 CH3 of TMS); 11B-NMR (CDCl3, 96 MHz): δ 30.6; FT-IR (neat) Іmax: 2978, 2166, 1562, 1352, 1143, 966, 927, 844, 760, 702 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 334 (8), 320 (100), 219 (10); HRMS (FAB): *m*/*z* 335.1407 [(M<sup>+</sup>); Calcd for C17H25BO2SiCl: 335.14055].

#### *3-(Phenylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-toluene (15)*

The general procedure B was applied to 3-bromotoluene (122 μL, 171 mg, 1.0 mmol, 1 equiv). The borylation step was carried out with HBpin (290 μL, 256 mg, 2.00 mmol, 2.00 equiv) for 12 h. The Sonogashira coupling step was carried out with phenyl acetylene (121 μL, 112 mg, 1.10 mmol, 1.1 equiv) for 12 h. Column chromatography (pentane/dichloromethane 1:1, R*<sup>f</sup>* 0.8) furnished the desired product as yellow oil, which solidified on standing (193 mg, 61% yield, mp 73–75 ◦C).

1H-NMR (CDCl3, 500 MHz): δ 7.83 (m, 1 H), 7.60 (m, 1 H), 7.47–7.50 (m, 2 H), 7.46 (m, 1 H), 7.30–7.34 (m, 3 H), 2.36 (s, 3 H), 1.36 (br s, 12 H, 4 CH3 of Bpin); 13C NMR {1H} (CDCl3, 75 MHz): δ 137.4 (C), 135.4 (CH), 135.4 (CH), 134.9 (CH), 131.7 (2 CH), 128.4 (2 CH), 128.2 (CH), 123.7 (C), 123.0 (C), 89.8 (C), 89.3 (C), 84.1 (2 C), 25.0 (4 CH3 of Bpin), 21.2 (CH3); 11B-NMR (C6D6, 96 MHz): δ 31.7; FT-IR (neat) Іmax: 2976, 1595, 1491, 1417, 1385, 1371, 1317, 1289, 1207, 1143, 966, 852, 756, 706, 690 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 318 (100), 304 (15), 233 (11), 219 (12); HRMS (FAB): *m*/*z* 318.1794 [(M<sup>+</sup>); Calcd for C21H23BO2: 318.1791].

## *3-(Phenylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-anisole (16)*

The general procedure B was applied to 3-bromoanisole (254 μL, 374 mg, 2.0 mmol, 1 equiv). The borylation step was carried out with HBpin (580 μL, 512 mg, 4.00 mmol, 2.00 equiv) for 16 h. The Sonogashira coupling step was carried out with phenyl acetylene (286 μL, 266 mg, 2.60 mmol, 1.3 equiv) for 4 h. Gradient column chromatography (hexanes/dichloromethane 1:1 → hexanes/dichloromethane 0:1) furnished the desired product as yellow oil (343 mg, 52% yield).

1H-NMR (CDCl3, 500 MHz): δ 7.61 (dd, *J* = 1.5, 0.9 Hz, 1 H), 7.54–7.49 (m, 2 H), 7.37–7.31 (m, 3 H), 7.30 (dd, *J* = 2.7, 0.9 Hz, 1 H), 7.15 (dd, *J* = 2.7, 1.5, Hz, 1 H), 3.85 (s, 3 H), 1.35 (br s, 12 H, 4 CH3 of Bpin); 13C-NMR {1H} (CDCl3, 125 MHz): δ 159.1 (C), 131.7 (2 CH), 130.8 (CH), 128.5 (2 CH), 128.3 (CH), 124.1 (C), 123.5 (C), 120.0 (CH), 119.8 (CH), 89.38 (C), 89.36 (C), 84.2 (2 C), 55.6 (OCH3), 25.0 (4 CH3 of Bpin); 11B NMR (CDCl3, 96 MHz): δ 30.6; FT-IR (neat) Іmax: 2980, 1581, 1373, 1224, 1143, 1057, 966,850, 756, 704 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 334 (100), 319 (10), 276 (6), 248 (15), 234 (21); HRMS (FAB): *m*/*z* 334.1742 [(M<sup>+</sup>); Calcd for C21H23BO3: 334.1740].

## *N,N-Di-methyl-3-(phenylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-aniline (17)*

The general procedure B was applied to N,N-dimethyl-3-bromoaniline (400 mg, 2.0 mmol, 1 equiv). The borylation step was carried out with HBpin (580 μL, 512 mg, 4.00 mmol, 2.00 equiv) for 24 h. The Sonogashira coupling step was carried out with phenyl acetylene (242 μL, 225 mg, 2.20 mmol, 1.1 equiv) for 20 h. Column chromatography (pentane/ether 4:1, R*<sup>f</sup>* 0.5) furnished the desired product as yellow oil (488 mg, 70% yield).

1H-NMR (C6D6, 300 MHz): δ 8.03 (dd, *J* = 1.4, 0.8 Hz, 1 H), 7.59–7.50 (m, 2 H), 7.48 (dd, *J* = 2.8, 0.8 Hz, 1 H), 7.12 (dd, *J* = 2.8, 1.4 Hz, 1 H), 7.06-6.96 (m, 3 H), 2.40 (s, 6 H), 1.15 (br s, 12 H, 4 CH3 of Bpin); 13C-NMR {1H} (C6D6, 75 MHz): δ 150.4 (C), 132.0 (2 CH), 128.6 (2 CH), 128.2 (CH), 127.6 (CH), 124.4 (C), 124.0 (C), 119.6 (CH), 118.4 (CH), 91.5 (C), 89.1 (C), 83.9 (2 C), 40.1 (2 CH3), 25.1 (4 CH3 of Bpin); 11B NMR (CDCl3, 96 MHz): δ 31.1; FT-IR (neat) Іmax: 2978, 2930, 2799, 1587, 1489, 1429, 1386, 1269, 1143, 1010, 966, 846, 756, 704, 690 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 347 (100), 289 (2), 247 (10); HRMS (FAB): *m*/*z* 347.2060 [(M<sup>+</sup>); Calcd for C22H26BNO2: 347.2057].
