*3-(Phenylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-chlorobenzene (18)*

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 (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 4:3, R*<sup>f</sup>* 0.8) furnished the desired product as a light yellow solid (117 mg, 37% yield, mp 45–46 ◦C).

1H-NMR (CDCl3, 300 MHz): δ 7.87 (dd, *J* = 1.6, 1.0 Hz, 1 H), 7.74 (dd, *J* = 2.2, 1.0 Hz, 1 H), 7.60 (dd, *J* = 2.2, 1.6 Hz, 1 H), 7.56–7.47 (m, 2 H), 7.40–7.32 (m, 3 H), 1.36 (br s, 12 H, 4 CH3 of Bpin); 13C NMR {1H} (CDCl3, 75 MHz): δ 136.2 (CH), 134.4 (CH), 134.1 (C), 133.8 (CH), 131.8 (2 CH), 128.7 (CH), 128.5 (2 CH), 124.9 (C), 123.1 (C), 90.7 (C), 88.2 (C), 84.5 (2 C), 25.0 (4 CH3 of Bpin); 11B NMR (CDCl3, 160 MHz): δ 29.9; FT-IR (neat) Іmax: 2978, 1562, 1412, 1356, 1142, 966, 862, 756, 700, 690 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 338 (100), 340(33), 324 (18), 280 (5), 252 (59); HRMS (FAB): *m*/*z* 338.1247 [(M<sup>+</sup>); Calcd for C20H20BClO2: 338.1245].
