1,3-diphenylprop-2-enyl acetate

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

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

Procedure: In 0.5 ml of dichloromethane were suspended 0.9 mg (2.5 μmol) of [PdCl(η3-C3H5)]2 and 1.8 mg (5.5 μmol) of (R,R)-t-Bu-QuinoxP* (1), followed by stirring at room temperature for 10 to 30 minutes. To the resulting solution were added a solution of 126 mg (0.50 mmol) of 1,3-diphenyl-2-propenyl acetate in 1.5 ml of dichloromethane, 171 μl (1.50 mmol) of dimethyl malonate, 367 μl (1.50 mmol) of N,O-bis(trimethylsilyl)acetamide (BSA), and a trace amount of potassium acetate. The reaction system was stirred at room temperature for 1 hour. The reaction mixture was diluted with diethyl ether, and a saturated aqueous solution of ammonium chloride was added to stop the reaction. The resulting mixture was extracted with diethyl ether, and the organic layer was washed with a sodium chloride aqueous solution. The organic layer was dried over anhydrous sodium sulfate. Any volatile matter was evaporated off, and the residue was purified by silica gel column chromatography. The reaction system was stirred at room temperature for 1 hour the reaction The resulting mixture was extracted with diethyl ether the organic layer was washed with a sodium chloride aqueous solution The organic layer was dried over anhydrous sodium sulfate Any volatile matter was evaporated off the residue was purified by silica gel column chromatography

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

Procedure: In 0.5 ml of dichloromethane were suspended 0.9 mg (2.5 μmol) of [PdCl(η3-C3H5)]2 and 1.8 mg (5.5 μmol) of (R,R)-t-Bu-QuinoxP* (1), followed by stirring at room temperature for 10 to 30 minutes. To the resulting solution were added a solution of 126 mg (0.50 mmol) of 1,3-diphenyl-2-propenyl acetate in 1.5 ml of dichloromethane, 171 μl (1.50 mmol) of dimethyl malonate, 367 μl (1.50 mmol) of N,O-bis(trimethylsilyl)acetamide (BSA), and a trace amount of potassium acetate. The reaction system was stirred at room temperature for 1 hour. The reaction mixture was diluted with diethyl ether, and a saturated aqueous solution of ammonium chloride was added to stop the reaction. The resulting mixture was extracted with diethyl ether, and the organic layer was washed with a sodium chloride aqueous solution. The organic layer was dried over anhydrous sodium sulfate. Any volatile matter was evaporated off, and the residue was purified by silica gel column chromatography. The reaction system was stirred at room temperature for 1 hour the reaction The resulting mixture was extracted with diethyl ether the organic layer was washed with a sodium chloride aqueous solution The organic layer was dried over anhydrous sodium sulfate Any volatile matter was evaporated off the residue was purified by silica gel column chromatography

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

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

Procedure: General procedure for the asymmetric Pd(0)-catalyzed allylic substitution reaction: To a Schlenk tube comprising (±) 1,3-dipheylprop-2-en-1-yl acetate (252 mg, 1.0 mmol), [Pd(allyl)Cl]2 (3.7 mg, 0.01 mmol, 1 mol %), was added (S, aR)-1,2,3,4-tetrahydro-2-methyl-1-(2-(diphenylphosphino)naphthalen-1-yl)isoquinoline (9.0 mg, 0.02 mmol, 2 mol %) in CH2Cl2 (2 mL). The reaction mixture was stirred at room temperature over a period of 30 minutes. Dimethyl malonate (396 mg, 3.0 mmol), KOAc (2.8 mg, 0.02 mmol) and BSA (613 mg, 3.0 mmol) were subsequently added at −78° C. The reaction mixture was stirred at −25° C. over a period of 48 hours, quenched using a saturated aqueous NH4Cl, solution and extracted with EtOAc (3×5 mL). The organic phase was washed with a saturated aqueous NaHCO3 solution, brine, dried using Na2SO4, and concentrated under reduced pressure. The residue was purified by means of flash chromatography on silica gel using hexane/EtOAc (6:1) as the eluent system to yield the desired product as a colorless oil (78% ee). 1H NMR (300 MHz, CDCl3): δ 3.54 (s, 3H), 3.70 (s, 3H), 3.96 (d, J=10.8 Hz, 1H), 4.25 (dd, J=10.8, 8.7 Hz, 1H), 6.33 (dd, J=15.4, 8.6 Hz, 1H), 6.46 (d, J=15.8 Hz, 1H), 7.17-7.24 (m, 10H). The enantiomeric purity (ee), as determined by means of chiral HPLC (Chiralpak AD, hexane/isopropanol=90:10, flow rate 1.0 mL/min); (tR=9.4 min., tS=12.7 min). To a Schlenk tube comprising The reaction mixture was stirred at −25° C. over a period of 48 hours quenched extracted with EtOAc (3×5 mL) The organic phase was washed with a saturated aqueous NaHCO3 solution, brine dried concentrated under reduced pressure The residue was purified by means of flash chromatography on silica gel

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

Procedure: In 0.5 ml of dichloromethane were suspended 0.9 mg (2.5 μmol) of [PdCl(η3-C3H5)]2 and 1.8 mg (5.5 μmol) of (R,R)-t-Bu-QuinoxP* (1), followed by stirring at room temperature for 10 to 30 minutes. To the resulting solution were added a solution of 126 mg (0.50 mmol) of 1,3-diphenyl-2-propenyl acetate in 1.5 ml of dichloromethane, 171 μl (1.50 mmol) of dimethyl malonate, 367 μl (1.50 mmol) of N,O-bis(trimethylsilyl)acetamide (BSA), and a trace amount of potassium acetate. The reaction system was stirred at room temperature for 1 hour. The reaction mixture was diluted with diethyl ether, and a saturated aqueous solution of ammonium chloride was added to stop the reaction. The resulting mixture was extracted with diethyl ether, and the organic layer was washed with a sodium chloride aqueous solution. The organic layer was dried over anhydrous sodium sulfate. Any volatile matter was evaporated off, and the residue was purified by silica gel column chromatography. The reaction system was stirred at room temperature for 1 hour the reaction The resulting mixture was extracted with diethyl ether the organic layer was washed with a sodium chloride aqueous solution The organic layer was dried over anhydrous sodium sulfate Any volatile matter was evaporated off the residue was purified by silica gel column chromatography

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