dichloro-di(propan-2-yl)silane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An oven-dried 100 mL-RB flask is charged with dichlorodiisopropylsilane (9.2 g, 0.05 mol). Then 15 g of trifluoromethanesulfonic acid (15 g, 0.10 mol) is added dropwise. The mixture is heated at 60° C. until no further HCl evolves. The residue is distilled to yield 12 g (60%) of the product as clear liquid. 1H NMR (500 MHz, CDCl3, in ppm) δ 1.58 (heptet, 2H, J=7.2 Hz), 1.24 (d, 12H, J=7.2 Hz). The residue is distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An oven-dried 100 mL-RB flask is charged with dichlorodiisopropylsilane (9.2 g, 0.05 mol). Then 15 g of trifluoromethanesulfonic acid (15 g, 0.10 mol) is added dropwise. The mixture is heated at 60° C. until no further HCl evolves. The residue is distilled to yield 12 g (60%) of the product as clear liquid. 1H NMR (500 MHz, CDCl3, in ppm) δ 1.58 (heptet, 2H, J=7.2 Hz), 1.24 (d, 12H, J=7.2 Hz). The residue is distilled

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of n-butyllithium (1.6M, 72.50 mL, 0.116 mol) was added slowly dropwise to a solution of bromo-4-methoxymethoxybenzene (25.23 g, 0.116 mol) in dry THF (110 mL) at −78° C. After stirring for 50 min at −78° C., dichlorodiisopropylsilane (21.00 mL, 0.116 mol) was charged into the flask. The reaction mixture was slowly allowed to warm to room temperature with stirring. Diethyl ether (100 mL) was added, the mixture was then stirred for 15 min and filtered. The filtrate was concentrated in vacuo to an oil. The oil was purified by short path distillation (116-128° C./0.18 mm Hg) to afford the compound (23.7 g, 71%) as a slightly cloudy pale yellow oil. to warm to room temperature with stirring the mixture was then stirred for 15 min filtered The filtrate was concentrated in vacuo to an oil The oil was purified by short path distillation (116-128° C./0.18 mm Hg)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of n-butyllithium (1.6M, 72.50 mL, 0.116 mol) was added slowly dropwise to a solution of bromo-4-methoxymethoxybenzene (25.23 g, 0.116 mol) in dry THF (110 mL) at −78° C. After stirring for 50 min at −78° C., dichlorodiisopropylsilane (21.00 mL, 0.116 mol) was charged into the flask. The reaction mixture was slowly allowed to warm to room temperature with stirring. Diethyl ether (100 mL) was added, the mixture was then stirred for 15 min and filtered. The filtrate was concentrated in vacuo to an oil. The oil was purified by short path distillation (116-128° C./0.18 mm Hg) to afford the compound (23.7 g, 71%) as a slightly cloudy pale yellow oil. to warm to room temperature with stirring the mixture was then stirred for 15 min filtered The filtrate was concentrated in vacuo to an oil The oil was purified by short path distillation (116-128° C./0.18 mm Hg)

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of benzyl alcohol (0.1 mL, 1.0 mmol) in THF (0.5 mL) was added dropwise to a cooled (−78° C.) solution of diisopropylethylamine (1 mL), dichlorodiisopropylsilane (0.3 mL, 1.62 mmol) in THF (4 mL). The solution was stirred for 3 h (−78→−20° C.). The mixture was cooled down to −78° C. and lithiumacetylid-ethylendiamin-complex (250 mg, 2.71 mmol) was added. The reaction mixture was stirred for 5 h (−78→20° C.). Water (4 mL) was added. The mixture was extracted with dichloromethane (20 mL). The organic phase was dried (Na2SO4) and concentrated. Compound 14a (100 mg, 41%) was obtained after flash chromatography. 1H-NMR (CDCl3): δ 7.4 (5H, 5×HC═), 5.0 (2H, CH2), 2.6 (1H, CH), 1.0 (14H, 2×CH, 2×CH3). The mixture was cooled down to −78° C. The reaction mixture was stirred for 5 h (−78→20° C.) The mixture was extracted with dichloromethane (20 mL) The organic phase was dried (Na2SO4) concentrated

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of benzyl alcohol (0.1 mL, 1.0 mmol) in THF (0.5 mL) was added dropwise to a cooled (−78° C.) solution of diisopropylethylamine (1 mL), dichlorodiisopropylsilane (0.3 mL, 1.62 mmol) in THF (4 mL). The solution was stirred for 3 h (−78→−20° C.). The mixture was cooled down to −78° C. and lithiumacetylid-ethylendiamin-complex (250 mg, 2.71 mmol) was added. The reaction mixture was stirred for 5 h (−78→20° C.). Water (4 mL) was added. The mixture was extracted with dichloromethane (20 mL). The organic phase was dried (Na2SO4) and concentrated. Compound 14a (100 mg, 41%) was obtained after flash chromatography. 1H-NMR (CDCl3): δ 7.4 (5H, 5×HC═), 5.0 (2H, CH2), 2.6 (1H, CH), 1.0 (14H, 2×CH, 2×CH3). The mixture was cooled down to −78° C. The reaction mixture was stirred for 5 h (−78→20° C.) The mixture was extracted with dichloromethane (20 mL) The organic phase was dried (Na2SO4) concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml-capacity, four-necked flask was charged with 18.5 g (0.1 moles) of diisopropyldichlorosilane and 17.6 g (0.1 moles) of diisopropyldimethoxysilane, and the resulting mixture was stirred at 20° C.-30° C. for 1 hour. There occurred a disproportionation reaction, thus giving a mixture comprising diisopropylmethoxychlorosilane, the unreacted diisopropyldichlorosilane and the unreacted diisopropyldimethoxysilane. a disproportionation reaction

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml-capacity, four-necked flask was charged with 18.5 g (0.1 moles) of diisopropyldichlorosilane and 17.6 g (0.1 moles) of diisopropyldimethoxysilane, and the resulting mixture was stirred at 20° C.-30° C. for 1 hour. There occurred a disproportionation reaction, thus giving a mixture comprising diisopropylmethoxychlorosilane, the unreacted diisopropyldichlorosilane and the unreacted diisopropyldimethoxysilane. a disproportionation reaction

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dichlorodiisopropylsilane 1 is treated with n-butyllithium in tetrahydrofuran solution to yield butyldiisopropyl-chlorosilane 2, which is then reacted with lithium (trimethylsilyl)acetylide in situ to yield trimethylsilyl protected ethynyl butyldiisopropylsilane 3. Selective removal of the TMS group with potassium carbonate affords ethynyl butyldiisopropylsilane 4. Using a standard procedure, this ethynyl silane is lithiated with n-butyllithium then reacted with commercial flavanthrone to yield the diol intermediate 5, which is reductive-aromatized under acidic conditions to afford 6.