## 2 Materials and Methods
### Synthesis and Characterization  
**2**: \(n\)-BuLi (1.25 mL, 2.0 mmol) was added dropwise to a solution of **1** (490 mg, 1.0 mmol) in THF (20 mL) at \(-\)110 \({}^{\circ}\)C. After stirring for 10 min, Me\({}_{2}\)SiCI\({}_{2}\) (134 \(\mu\)L, 1.1 mmol) was added at \(-\)78 \({}^{\circ}\)C and the resulting suspension was allowed to warm quickly to room temperature and stirred overnight at room temperature. After evaporation of the solvent, **2** was purified by column chromatography on silica (petroleum ether) and recrystallized from hexane to give white crystals (75 mg, 0.26 mmol, 26% yield). \({}^{1}\)H NMR (300 MHz, CDCl\({}_{3}\)): \(\delta\) = 0.60 (s, 6H, CH\({}_{3}\)), 7.22-7.29 (m, 4H, Ar-H), 7.51-7.60 (m, 4H, Ar-H); \({}^{13}\)C NMR (75 MHz, CDCl\({}_{3}\)): \(\delta\) = -3.5 (CH\({}_{3}\)), 112.1 (CH), 117.4 (C\({}_{\text{quat}}\)), 121.5 (CH), 123.8 (CH), 124.0 (CH), 130.6 (C\({}_{\text{quat}}\)), 158.5 (C\({}_{\text{quat}}\)), 159.0 (C\({}_{\text{quat}}\)). \({}^{29}\)Si NMR (80 MHz, CDCl\({}_{3}\)): \(\delta\) = \(-\)12.5 (s). HRMS Calcd for C\({}_{18}\)H\({}_{14}\)O\({}_{2}\)Si(M\({}^{+}\)): 290.0763; Found: 290.0760. Anal. Calcd. for C\({}_{18}\)H\({}_{14}\)O\({}_{2}\)Si (C, 74.45, H, 4.86); Found: C, 74.43, H, 4.70. **3**: \(n\)-BuLi (1.25 mL, 2.0 mmol) was added dropwise to a solution of **1** (490 mg, 1.0 mmol) in THF (20 ml) at \(-\)110 \({}^{\circ}\)C. After stirring for 10 min, the resulting solution was cannulated into a solution of SiCI\({}_{4}\) (460 \(\mu\)L, 4 mmol) in THF (10 mL) at \(-\)78 \({}^{\circ}\)C. The reaction mixture was stirred at room temperature overnight. Then the solvents were removed by vacuum, and the resultant reactive intermediate **3** was used in situ for the synthesis of siloles **4-6** without isolation. **4**: To a 25 mL flask was added 5 mL Et\({}_{2}\)O, magnesium shavings (72 mg, 3 mmol), bromobenzene (324 \(\mu\)L, 3 mmol), iodine and the mixture was stirred at 40 \({}^{\circ}\)C for 2 h. The gray suspension was slowly transferred into a THF solution of **3** at \(-\)78 \({}^{\circ}\)C. The brown mixture was gradually warmed to room temperature, and stirred overnight. The solvent was removed, and the residue was purified by column chromatography on silica (hexane/DCM = 5/1) and recrystallized from hexane and DCM to afford white crystals (165 mg, 0.4 mmol, 40% yield). \({}^{1}\)H NMR (300 MHz, CDCl\({}_{3}\)): \(\delta\) = 7.28-7.44 (m, 10H), 7.60-7.68 (m, 4H), 7.76-7.77 (m, 4H); \({}^{13}\)C NMR (75 MHz, CDCl\({}_{3}\)): \(\delta\) = 112.3 (CH), 115.3 (C\({}_{\text{quat}}\)), 121.7 (CH), 124.4 (CH), 128.5 (CH), 130.5 (C\({}_{\text{quat}}\)), 130.7 (CH), 130.8 (C\({}_{\text{quat}}\)), 135.3 (CH), 158.7 (C\({}_{\text{quat}}\)), 159.9 (C\({}_{\text{quat}}\)). \({}^{29}\)Si NMR (80 MHz, CDCl\({}_{3}\)): \(\delta\) = \(-\)21.6 (s). HRMS Calcd for C\({}_{28}\)H\({}_{18}\)O\({}_{2}\)Si(M\({}^{+}\)): 414.1076; Found: 414.1074. Anal. Calcd. for C\({}_{28}\)H\({}_{18}\)O\({}_{2}\)Si(C, 81.13, H, 4.38); Found: C, 81.49, H, 4.17. **5**: To a 25 mL flask was added 5 mL Et\({}_{2}\)O, magnesium shavings (72 mg, 3 mmol), 4-bromoanisole (375 \(\mu\)L, 3 mmol), iodine, and the mixture was stirred at 40 \({}^{\circ}\)C for 2 h. The gray suspension was slowly transferred portion wisely into the THF solution of **3** at \(-\)78 \({}^{\circ}\)C. The brown mixture was gradually warmed to room temperature, and stirred overnight. The solvent was removed, and the residue was purified by column chromatography on silica (hexane/DCM = 5/1) and recrystallized from hexane and DCM to afford white crystals (147 mg, 0.31 mmol, 31% yield).