butyl-chloro-dimethylsilane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2.3 g (12.6 mMol) of (4aR,5S,8aS)-5-hydroxy-8a-methyl-octahydro-naphtalen-1-one in 63 ml of dimethylformamide are added under stirring and argon atmosphere 3.74 g (24.8 mMol) of tertio-butyl-dimethyl-silylchloride and 1.94 g (28.5 mMol) of imidazole. The reaction mixture is heated to 100° C. for 4 hours, then additional 3.74 g of tert-butyl-dimethylsilylchloride and 1.94 g of imidazole are added and the reaction mixture is kept overnight at 100° C. The reaction mixture is poured onto ice-water and extracted three times with diethylether. The combined organic extract is washed once with water and brine, dried over sodium sulfate and evaporated in vacuo. The residue is chromatographed over 250 g of silicagel with hexane/ethylacetate 9/1 to yield 3.17 g (85%) of low melting cristalline (4aR,5S,8aS)-5-(tert-butyl-dimethyl-silanyloxy)-8a-methyl-octahydro-naphtalen-1-one. The reaction mixture is poured onto ice-water extracted three times with diethylether The combined organic extract is washed once with water and brine dried over sodium sulfate evaporated in vacuo The residue is chromatographed over 250 g of silicagel with hexane/ethylacetate 9/1

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: i-propylmagnesiumbromide (0.67 M/THF solution, 3.10 mL, 2.1 mmol) was added dropwise to THF solution (15 mL) of 1-bromo-4-ethynylbenzene (382 mg, 2.0 mmol) at 0° C. After the mixture was stirred for 20 minutes, an ice water bath was removed. After stirring at room temperature for 10 minutes, n-butyldimethylsilyl chloride (0.69 mL, 4.0 mmol) was added to the mixture. After stirring for 2 hours, the reaction was terminated by the addition of saturated ammonium chloride solution (5 mL). The reaction mixture was extracted with ethyl acetate, and it was concentrated and thereafter purified by means of flash column chromatography to obtain (4-bromophenylethynyl)-n-butyldimethylsilane (530 mg, isolated yield: 90%). an ice water bath was removed After stirring at room temperature for 10 minutes After stirring for 2 hours the reaction was terminated by the addition of saturated ammonium chloride solution (5 mL) The reaction mixture was extracted with ethyl acetate, and it was concentrated purified by means of flash column chromatography

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: (R)-2-Bromo-1-(3-formamido-4-benzyloxyphenyl)ethanol (9.9 g, 28 mmol) was dissolved in dimethylformamide (36 mL). Imidazole (2.3 g, 34 mmol) and tert-butyldimethylsilyl chloride (4.7 g, 31 mmol) were added. The solution was stirred under nitrogen atmosphere for 72 h. Additional imidazole (0.39 g, 5.7 mmol) and tent-butyldimethylsilyl chloride (0.64 g, 4.3 mmol) were added and the reaction was stirred for an additional 20 h. The reaction mixture was then diluted with a mixture of isopropyl acetate (53 mL) and hexanes (27 mL) and transferred to a separatory funnel. The organic layer was washed twice with a mixture of water (27 mL) and saturated aqueous sodium chloride (27 mL) followed by a final wash with saturated aqueous sodium chloride (27 mL). The organic layer was dried over sodium sulfate. Silica gel (23.6 g) and hexanes (27 mL) were added and the suspension was stirred for 10 min. The solids were removed by filtration and the filtrate concentrated under vacuum. The residue was crystallized from hexanes (45 mL) to afford 8.85 g (19 mmol, 68%) of the title compound as a solid. MS m/z: [M+H+] calcd for C22H30NO3SiBr 464.1; found 464.2. the reaction was stirred for an additional 20 h transferred to a separatory funnel The organic layer was washed twice with a mixture of water (27 mL) and saturated aqueous sodium chloride (27 mL) a final wash with saturated aqueous sodium chloride (27 mL) The organic layer was dried over sodium sulfate Silica gel (23.6 g) and hexanes (27 mL) were added the suspension was stirred for 10 min The solids were removed by filtration the filtrate concentrated under vacuum The residue was crystallized from hexanes (45 mL)