*3-(Trimethylsilylethynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-benzonitrile (20)*

The general procedure B was applied to 3-bromobenzonitrile (182 mg, 1.0 mmol, 1 equiv). The borylation step was carried out with B2pin2 (153 mg, 0.60 mmol, 1.2 equiv of boron), [Ir(OMe)(COD)]2 (10 mg, 0.015 mmol, 3 mol % Ir), and dtbpy (8 mg, 0.03 mmol, 3 mol %) at room temperature for 2 h. The Sonogashira coupling step was carried out with trimethylsilyl acetylene (156 μL, 108 mg, 1.10 mmol, 1.1 equiv) for 2 h. Column chromatography (pentane/ethylacetate 9:1, R*<sup>f</sup>* 0.7) furnished the desired product as yellow oil (154 mg, 47% yield).

1H-NMR (CDCl3, 500 MHz): δ 8.07 (dd, *J* = 1.7, 1.1 Hz, 1 H), 7.98 (dd, *J* = 1.7, 1.1 Hz, 1 H), 7.77 (t, *J* = 1.7 Hz, 1 H), 1.34 (br s, 12 H, 4 CH3 of Bpin), 0.24 (s, 9 H, 3 CH3 of TMS); 13C-NMR {1H} (CDCl3, 125 MHz): δ 142.1 (CH), 137.7 (CH), 137.3 (CH), 124.3 (C), 118.1 (C), 112.5 (C), 102.5 (C), 97.3 (C), 84.8 (2 C), 25.0 (4 CH3 of Bpin), <sup>−</sup>0.1 (3 CH3 of TMS); 11B-NMR (CDCl3, 96 MHz): <sup>δ</sup> 30.4; FT-IR (neat) Іmax: 2961, 2235, 2158, 1589, 1369, 1250, 1143, 968, 954, 846, 760, 700 cm<sup>−</sup>1; GC-MS (EI) *m*/*z* (% relative intensity): M<sup>+</sup> 325 (3), 311 (100), 210 (3); HRMS (FAB): *m*/*z* 326.1748 [(M<sup>+</sup>); Calcd for C18H25BO2SiN: 326.17477].
