Allylbenzene

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

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

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

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: 0.80 g (2.7 mmol) of methyl 2-chloro-3-hydroximinomethyl-4-methylsulfonylbenzoate are dissolved in 20 ml of dimethylformamide with 0.38 g (2.9 mmol) of N-chlorosuccinimide. After stirring at room temperature for 4 hours, 0.49 g (2.9 mmol) of allylbenzene and then 0.29 g (2.9 mmol) of triethylamine are added dropwise at 0° C. After stirring at room temperature for 16 hours, the reaction mixture is concentrated in a rotary evaporator, the residue is dissolved in dichloromethane and the solution is washed with sodium bicarbonate solution and with water. After drying over magnesium sulfate and evaporating the solvent, 1.1 g (100% of theory) of methyl 2-chloro-3-(5-benzylisoxazolin-3-yl)-4-methylsulfonylbenzoate are obtained as a colorless oil. After stirring at room temperature for 16 hours the reaction mixture is concentrated in a rotary evaporator the residue is dissolved in dichloromethane the solution is washed with sodium bicarbonate solution and with water After drying over magnesium sulfate evaporating the solvent, 1.1 g (100% of theory) of methyl 2-chloro-3-(5-benzylisoxazolin-3-yl)-4-methylsulfonylbenzoate are obtained as a colorless oil

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

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

Procedure: A solution of m-chloroperbenzoic acid (mCPBA; 17 g, 0.1 mol) in 120 mL of methylene chloride was added (at ambient temperature) dropwise to a solution of allyl benzene (10 g, 85 mmol) in 200 mL of methylene chloride. After the reaction mixture was stirred for 5 h with a mechanical stirrer, 5 additional grams of m-CPBA were added and the reaction mixture stirred for another 2 h. The reaction mixture was then diluted with 200 mL of ether, washed with 2×100 mL of aqueous sodium bisulfite solution, 1×100 mL of aqueous sodium bicarbonate solution and 1×100 mL of brine. The organic solution was dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by bulb-to-bulb distillation (60° C., 0.1 mm) to give 8.5 g (77% yield) of 1-benzyl ethylene oxide as a clear colorless liquid. the reaction mixture stirred for another 2 h washed with 2×100 mL of aqueous sodium bisulfite solution, 1×100 mL of aqueous sodium bicarbonate solution and 1×100 mL of brine The organic solution was dried over anhydrous magnesium sulfate filtered concentrated in vacuo The residue was purified by bulb-to-bulb distillation (60° C., 0.1 mm)

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

Procedure: A solution of m chloroperbenzoic acid (mCPBA; 17 g, 0.1 mol) in 120 mL of methylene chloride was added (at ambient temperature) dropwise to a solution of allyl benzene (10 g, 85 mmol) in 200 mL of methylene chloride. After the reaction mixture was stirred for 5 h with a mechanical stirrer, 5 additional qrams of m CPBA were added and the reaction mixture stirred for another 2 h. The reaction mixture was then diluted with 200 mL of ether, washed with 2×100 mL of aqueous sodium bisulfite solution, 1×100 mL of aqueous sodium bicarbonate solution and 1×100 mL of brine. The organic solution was dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by bulb-to-bulb distillation (60° C., 0.1 mm) to give 8.5 g (77% yield) of 1-benzyl ethylene oxide as a clear colorless liquid. 5 additional qrams of m CPBA were added the reaction mixture stirred for another 2 h washed with 2×100 mL of aqueous sodium bisulfite solution, 1×100 mL of aqueous sodium bicarbonate solution and 1×100 mL of brine The organic solution was dried over anhydrous magnesium sulfate filtered concentrated in vacuo The residue was purified by bulb-to-bulb distillation (60° C., 0.1 mm)

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

Procedure: To a solution of allylbenzene (106 mg, 0.89 mmol) in 0.5 mL of THF was added 9-BBN (0.89 mmol, 1 eguiv) in THF, at 0°. Let stir for 1 h, warming to 5°. To the mixture was added (+)-(4aR)-(10bR)-8-bromo-10b-methyl-1,2,3,4,4a,5,6,10b-octahydrobenzo[f]quinolin-3-one (250 mg, 0.812 mmol), triphenyl phosphine (42 mg, 0.16 equiv.), tetrakis(triphenylphosphine) palladium(0) (19 mg, 0.02 equiv.), 1 mL of 3N sodium hydroxide solution and an additional 1 mL of THF. The resulting mixture was heated at 80° for 18 h, cooled, and ethanolamine was added, followed by ethyl acetate. The resulting organic phase was washed with brine, dried over sodium sulfate, concentrated, and purified by silica gel chromatography (50-100% ethyl acetate/hexanes eluent gradient) to give 160 mg (59%) of the title compound as an oil. FDMS m/e=347. at 0° warming to 5° The resulting mixture was heated at 80° for 18 h cooled The resulting organic phase was washed with brine dried over sodium sulfate concentrated purified by silica gel chromatography (50-100% ethyl acetate/hexanes eluent gradient)

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

Procedure: To a solution of allylbenzene (106 mg, 0.89 mmol) in 0.5 mL of THF was added 9-BBN (0.89 mmol, 1 eguiv) in THF, at 0°. Let stir for 1 h, warming to 5°. To the mixture was added (+)-(4aR)-(10bR)-8-bromo-10b-methyl-1,2,3,4,4a,5,6,10b-octahydrobenzo[f]quinolin-3-one (250 mg, 0.812 mmol), triphenyl phosphine (42 mg, 0.16 equiv.), tetrakis(triphenylphosphine) palladium(0) (19 mg, 0.02 equiv.), 1 mL of 3N sodium hydroxide solution and an additional 1 mL of THF. The resulting mixture was heated at 80° for 18 h, cooled, and ethanolamine was added, followed by ethyl acetate. The resulting organic phase was washed with brine, dried over sodium sulfate, concentrated, and purified by silica gel chromatography (50-100% ethyl acetate/hexanes eluent gradient) to give 160 mg (59%) of the title compound as an oil. FDMS m/e=347. at 0° warming to 5° The resulting mixture was heated at 80° for 18 h cooled The resulting organic phase was washed with brine dried over sodium sulfate concentrated purified by silica gel chromatography (50-100% ethyl acetate/hexanes eluent gradient)

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

Procedure: Following the general procedure, allyl benzene (50.0 mg, 0.423 mmol, 7) was treated with p-methoxyphenyl vinyl ether (127 mg, 8.46 mmol) and 1.2 mol % of in situ-generated complex la (51.0 μL, 0.10 M, 5.08 μmol; final substrate concentration=8.3 M) and allowed to stir for 16 h. The unpurified product is >98% Z (as determined by 400 MHz 1H NMR analysis). Excess p-methoxyphenyl vinyl ether was removed by vacuum distillation (1.0 torr, 80° C.). The resulting oil was purified by neutral alumina chromatography (100% hexanes to 100:1 hexanes:Et2O) to afford 10a (56.8 mg, 0.236 mmol, 56.0% yield, >98% Z isomer) as a colorless oil. IR (neat): 3027 (w), 3000 (w), 2950 (w), 2908 (w), 2834 (w), 1664 (m), 1502 (s), 1464 (m), 1453 (m), 1441 (m), 1384 (m), 1212 (s), 1179 (m), 1088 (m), 1064 (m), 1034 (m), 989 (m); NMR (400 MHz, CDCl3): δ 7.33-7.25 (4H, m), 7.24-7.18 (1H, m), 7.01-6.95 (2H, m), 6.89-6.84 (2H, m), 6.42 (1H, dt, J=6.0, 1.6 Hz), 4.96 (1H, td, J=7.6, 6.0 Hz), 3.80 (3H, s), 3.58 (2H, dd, J=7.6, 1.2 Hz); 13C NMR (100 MHz, CDCl3): δ 155.4, 151.7, 141.9, 141.2, 128.6, 128.5, 126.0, 117.6, 114.8, 110.6, 55.9, 30.4; HRMS (ESI+) [M+NH4]+ calcd for C16H20NO2. 258.1494, found: 258.1491. Excess p-methoxyphenyl vinyl ether was removed by vacuum distillation (1.0 torr, 80° C.) The resulting oil was purified by neutral alumina chromatography (100% hexanes to 100:1 hexanes:Et2O)