| 95% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at -78 - 20℃; for 0.5h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at -78 - 20℃; for 3h; Inert atmosphere; |
|
| 90% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran |
|
| 88% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.0833333h;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 3℃; for 3h; |
1
o a suspension of methyltriphenyl phosphonium bromide (108g, 303 mmol) in THF (75OmL) at room temperature was added KO1Bu (112.24g, 303 mmol) in portions. After being stirred for 5min, the reaction mixture was treated with 2'bromoacetophenone (50.3g, 253 mmol). The reaction mixture was stirred for 3hrs at room temperature then quenched with saturated ammonium chloride. Extracted 3X with Et2O and the combined organic layers were washed with brine, dried over MgSO4 and evaporated under vacuum. Purified by silica gel chromatography (100% petroleum ether) to give 43.8g (88%) of l-bromo-2-(prop-l-en-2-yl)benzene as a colorless oil. |
| 88% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; Inert atmosphere; |
|
| 88% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; Inert atmosphere; |
To the mixture of methyltriphenylphosphonium bromide (21.6 g, 60.0 mmol) and t-BuOK (9.0 g, 80.0 mmol) was added anhydrous THF (80.0 mL) and stirred at r.t. for 1 hour under argon, then a solution of 1-(2-bromophenyl)ethan-1-one (8.0 g, 40.0 mmol) in THF (40.0 mL) was added dropwise. The resulting reaction mixture was stirred overnight at room temperature and quenched with saturated NH4Cl solution. The organic layer was separated and the aqueous layer was extracted with EtOAc (3 × 30 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel using petroleum/EtOAc as eluent to yield 1-bromo-2-(prop-1-en-2-yl)benzene (6.9 g, 88%) |
| 88% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Schlenk technique;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran Inert atmosphere; |
4 Example 4:(1S,3S,3'S)-3,3'-dimethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[benzo[b]thiole](Id) Synthesis
In a nitrogen atmosphere, methyltriphenylphosphonium bromide (21.4g, 60mmol) and potassium tert-butoxide (8.4g, 75mmol) and 50mL of tetrahydrofuran in a 200mL dry Schlenk bottle, after stirring at room temperature for 0.5h, will be dissolved 1-(2-bromophenyl)ethanone (9.6g, 48.2mmol)The tetrahydrofuran (20mL) solution was added dropwise to the previous system, and the reaction was detected by TLC.Saturated aqueous ammonium chloride solution was added dropwise to quench the reaction, and extracted three times with ethyl acetate,The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and allowed to stand.Remove the desiccant by suction filtration,The filtrate was removed with a rotary evaporator and purified by column chromatography to obtain 1-bromo-2-(prop-1-en-2-yl)benzene(8.3g, yield: 88%). |
| 83% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.25h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; |
|
| 79% |
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; Inert atmosphere; Schlenk technique;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran; hexane at 0 - 20℃; Inert atmosphere; Schlenk technique; |
|
| 73% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone at 20℃; Inert atmosphere; |
|
| 71% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 10℃; for 2h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone at 0 - 5℃; for 16h; |
12.1 Step 1: 1 -bromo-2-(prop-1 -en-2-yl)benzene
Step 1: 1-bromo-2-(prop-1-en-2-yl)benzene Potassium tert-butanolate (t-BuOK) (21.1 g, 0.188 mol) was suspended in THF (250 mL) under nitrogen. The suspension was cooled down in ice-bath to keep the inner temperature below 10° C., and then added methyltriphenylphosphonium bromide (67.3 g, 0.188 mol) in small portions. The resulted mixture was kept below 10° C. and stirred for 2 h. After this, the mixture was cooled down to 0° C. and added 1-(2-bromophenyl)ethanone (25 g, 0.126 mol), the inner temperature was kept below 5° C. during this period. The resulted mixture was stirred for 16 h, and then added H2O (250 mL), and then extracted with ethyl acetate (200 mL*3). The combined organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated under vacuum to afford 1-bromo-2-(prop-1-en-2-yl)benzene (18.1 g, yield: 71%) as light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.58 (dd, J=7.6, 1.2 Hz, 1H), 7.27-7.31 (m, 1H), 7.21-7.23 (m, 1H), 7.12-7.16 (m, 1H), 5.26 (m, 1H), 4.97 (m, 1H), 2.13 (s, 3H). |
| 71% |
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran; hexane at 20℃; Inert atmosphere; |
|
| 67% |
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran; hexane at 0 - 60℃; Inert atmosphere; |
|
| 65% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 2h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 16.5h; Inert atmosphere; |
General synthesis procedure of the methylene compounds 1 (1f - 1p)1
General procedure: t-BuOK (2.47 g, 22.00 mmol) was added in four portions to a solution of methyltriphenylphosphonium bromide (7.12 g, 20.00 mmol) in dry THF (70 mL) at 0 oC. The mixture was stirred at 0 oC for 2 h and then acetophenone derivatives (20 mmol) in dry THF (20 mL) was added dropwise in 30 minutes. After stirred at room temperature for another 16 h, the mixture was quenched with saturated NH4Cl (50 mL). The solution was extracted three times with petroleum ether (3 × 50 mL). The combined organic phases were washed with brine (50 mL), dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by flash column chromatography with petroleum ether (Pet) as eluent to afford the corresponding α-Methylstryrene derivatives. |
| 64% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 36h; Inert atmosphere; |
|
| 60% |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran for 0.333333h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran Inert atmosphere; |
|
| 44% |
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In diethyl ether; hexane at 0℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In diethyl ether; hexane at 0 - 20℃; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In diethyl ether; hexane for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In diethyl ether; hexane at 20℃; for 24h; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran for 2h; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5h; Inert atmosphere; Schlenk technique;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran; hexane at 0℃; for 2h; Inert atmosphere; Schlenk technique; |
|
|
With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 16h; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With sodium t-butanolate In tetrahydrofuran at 0℃; Inert atmosphere; Schlenk technique; Sealed tube;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 0 - 20℃; for 17h; Inert atmosphere; Schlenk technique; Sealed tube; |
|
|
With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 12h; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.75h;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 16h; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 2h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 10h; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.75h;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 16h; |
|
|
With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 16h; Inert atmosphere; |
|
|
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere;
Stage #2: 2-bromophenyl methyl ketone In tetrahydrofuran at 20℃; for 6h; Inert atmosphere; |
|
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