3.2. Synthetic procedures of compounds 6-15
An argon-purged three necked flask equipped with a magnetic stirring bar and an addition funnel was charged with all-cis-[ViSi(OK)O]4 (0.5 g, 1.0 mmol), anhydrous THF (20 mL), and distilled Et3N (0.42 mL, 3.0 mmol). A solution of dichlorodivinylsilane (0.42 mL, 3.0 mmol) in anhydrous THF (45 mL) was introduced into the addition funnel under an argon atmosphere. Then, a solution of dichlorodivinylsilane was added dropwise to the flask at 0 ℃. After the addition, the reaction mixture was stirred at 25 ˚C for 1 h. Then, a saturated NH4Cl aqueous solution was added to the reaction medium to neutralize Et3N, and chloroform was added to extract the product three times. The gathered organic layer was then washed with brine three times, dried over anhydrous Na2SO4, and concentrated on a rotary evaporator to afford the crude product as a slightly yellow viscous oil, which was purified by GPC (CHCl3) to give pure product 6 as a colorless solid (0.15 g, 0.30 mmol, 30%).
An argon-purged, three necked, round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with all-cis-[ViSi(OK)O]4 (0.5 g, 1.0 mmol), anhydrous THF (20 mL), and distilled Et3N (0.42 mL, 3.0 mmol). A solution of diallyldichlorosilane (0.51 mL, 3.0 mmol) in anhydrous THF (45 mL) was introduced into the addition funnel under an argon atmosphere. Then, a solution of diallyldichlorosilane was added dropwise to the flask at 0 ℃. The reaction mixture was stirred at 25 ˚C for 1 h. Then, a saturated NH4Cl aqueous solution was added to the reaction medium to neutralize Et3N, and chloroform was added to extract the product three times. The gathered organic layer was then washed with brine three times, dried over anhydrous Na2SO4, and concentrated on a rotary evaporator to afford the crude colorless product as a colorless viscous oil, which was purified by GPC (CHCl3) to give pure product 7 as a colorless liquid (0.30 g, 0.53 mmol, 53%).
An argon-purged three necked flask equipped with a magnetic stirring bar and an addition funnel was charged with all-cis-[ViSi(OK)O]4 (0.5 g, 1.0 mmol), anhydrous THF (25 mL), and distilled Et3N (0.56 mL, 3.75 mmol). A solution of dichloromethylvinylsilane (0.39 mL, 3.0 mmol) in anhydrous THF (45 mL) was introduced into the addition funnel under an argon atmosphere. Then, a solution of dichloromethylvinylsilane was added dropwise to the flask at 0 ℃. The reaction mixture was stirred at 25 ˚C for 1 h. Then, a saturated NH4Cl aqueous solution was added into the reaction medium to neutralize Et3N, and chloroform was added to extract the product three times. The gathered organic layer was then washed with brine three times, dried over anhydrous Na2SO4, and concentrated on a rotary evaporator to afford the crude as a slightly yellow viscous oil, which was purified by GPC (CHCl3) to give product 8 as a colorless solid (0.20 g, 0.4 mmol, 41%).
An argon-purged three necked flask equipped with a magnetic stirring bar and an addition funnel was charged with all-cis-[ViSi(OK)O]4 (0.5 g, 1.0 mmol), anhydrous THF (20 mL), and distilled Et3N (0.51 mL, 3.0 mmol). A solution of dichlorophenylvinylsilane (0.39 mL, 3.0 mmol) in anhydrous THF (45 mL) was introduced into the addition funnel under an argon atmosphere. Then, a solution of dichlorophenylvinylsilane was added dropwise to the flask at 0 ℃. The reaction mixture was stirred at 25 ˚C for 1 h. Then, a saturated NH4Cl aqueous solution was added into the reaction medium to neutralize Et3N, and chloroform was added to extract the product three times. The gathered organic layer was then washed with brine three times, dried over anhydrous Na2SO4, and concentrated on a rotary evaporator to afford the crude product as white wax, which was purified by GPC (CHCl3) to give pure product 9 as a colorless solid (0.166 g, 27%).
An argon-purged Schlenk equipped with a stir bar was charged with 6 (0.026 g, 0.05 mmol), anhydrous toluene (0.3 mL), and dimethylphenylsilane (92 µL, 0.6 mmol). Karstedt’s catalyst (2% Pt, commercial bottle, diluted 100 times in anhydrous toluene under argon, 115 μL, 0.1 μmol Pt) was added to the mixture under an argon atmosphere at 25 °C. After addition, the mixture was heated to 100 °C and stirred at 100 ˚C for 20 h. After the reaction, the mixture was cooled to room temperature and passed through a silica plug, which was then washed with toluene and dichloromethane. The solvents were removed using a rotary evaporator to afford the crude product as a viscous colorless oil (87 mg). The crude product was purified using GPC (eluent: CHCl3), and pure product 10 was obtained as a colorless liquid (66 mg, 82%).
An argon-purged Schlenk equipped with a stir bar was charged with 7 (0.028 g, 0.050 mmol), anhydrous toluene (0.30 mL), and dimethylphenylsilane (92 µL, 0.60 mmol). Karstedt’s catalyst (2% Pt, commercial bottle, diluted 100 times in anhydrous toluene under argon, 115 μL, 0.1 μmol Pt) was added to the mixture under an argon atmosphere at 25 °C. After addition, the mixture was heated to 65 °C and stirred at 65 °C for 18 h. After the reaction, the mixture was cooled to room temperature and passed through a silica plug, which was then washed with toluene and dichloromethane. The solvents were removed using a rotary evaporator to obtain viscous brown oil (90 mg). The crude product was purified using GPC (CHCl3), and pure product 11 was obtained as a colorless liquid (32 mg, 40%).
An argon-purged Schlenk equipped with a stir bar was charged with 8 (0.024 g, 0.05 mmol), anhydrous toluene (0.3 mL), and dimethylphenylsilane (61 µL, 0.45 mmol). Karstedt’s catalyst (2% Pt, commercial bottle, diluted 100 times in anhydrous toluene under argon, 57 μL, 0.05 μmol Pt) was added to the mixture under an argon atmosphere at 25 °C. After addition, the mixture was heated to 65 °C and stirred at 65 ˚C for 18 h. After the reaction, the mixture was cooled to room temperature and passed through a silica plug, which was then washed with toluene and dichloromethane. The solvents were removed using a rotary evaporator to afford pure product 12 as viscous yellow oil (64 mg, 99%).
An argon-purged Schlenk equipped with a stir bar was charged with 7 (0.028 g, 0.050 mmol), anhydrous toluene (0.30 mL), and chloromethyl(dimethyl)silane (73 µL, 0.60 mmol). Karstedt’s catalyst (2% Pt, commercial bottle, diluted 100 times in anhydrous toluene under argon, 115 μL, 0.1 μmol Pt) was added to the mixture under an argon atmosphere at 25 °C. After addition, the mixture was heated to 40 °C and stirred at 40 °C for 18 h. After the reaction, the mixture was cooled to room temperature and passed through a silica plug, which was then washed with toluene and dichloromethane. The solvents were removed using a rotary evaporator to give 13 as a colorless solid (42 mg, 60%).
An argon-purged Schlenk equipped with a stir bar was charged with 8 (0.024 g, 0.05 mmol), anhydrous toluene (0.3 mL), and chloromethyl(dimethyl)silane (55 µL, 0.45 mmol). Karstedt’s catalyst (2% Pt, commercial bottle, diluted 100 times in anhydrous toluene under argon, 57 μL, 0.05 μmol Pt) was added to the mixture under an argon atmosphere at 25 °C. After addition, the mixture was heated to 40 °C and stirred at 40 ˚C for 18 h. After the reaction, the mixture was cooled to room temperature and passed through a silica plug, which was then washed with toluene and dichloromethane. The solvents were removed using a rotary evaporator to afford pure product 14 as viscous colorless oil (57 mg, 99%).
An argon-purged Schlenk equipped with a stir bar was charged with 7 (0.056 g, 0.1 mmol), anhydrous toluene (0.3 mL), and dimethylphenylsilane (92 µL, 0.6 mmol). Karstedt’s catalyst (2% Pt, commercial bottle, diluted 100 times in anhydrous toluene under argon, 57 μL, 0.05 μmol Pt) was added to the mixture under an argon atmosphere at 25 °C. After addition, the mixture was heated to 65 °C and stirred at 65 ˚C for 18 h. After the reaction, the mixture was cooled to room temperature and passed through a silica plug, which was then washed with toluene and dichloromethane. The solvents were removed using a rotary evaporator to afford crude product 15 as viscous yellow oil (135 mg).