ethyl 2-phenylcyclopropane-1-carboxylate

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

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

Procedure: The reaction described in Example 3 was substantially repeated except that the Cu,K-PFIEP[SO3H] catalyst was replaced by the Cu,K-PFIEP[SO3H]/PFIEP[CO2H] (0.58 g) catalyst described above. The reaction mixture was allowed to stir for 0.5 hour after the addition of the solution of ethyl diazoacetate, CH2Cl2 and styrene. Analysis by gas chromatography showed that the combined yield of cis- and trans-ethyl-2-phenylcyclopropanecarboxylates was 95%.

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

Procedure: The reaction described in Example 3 was substantially repeated except that the Cu,K-PFIEP[SO3H] catalyst was replaced by the Cu,K-PFIEP[SO3H]/PFIEP[CO2H] (0.58 g) catalyst described above. The reaction mixture was allowed to stir for 0.5 hour after the addition of the solution of ethyl diazoacetate, CH2Cl2 and styrene. Analysis by gas chromatography showed that the combined yield of cis- and trans-ethyl-2-phenylcyclopropanecarboxylates was 95%.

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

Procedure: A solution of CH2Cl2 (12.5 mL), styrene (12 5 mL) and ethyl diazoacetate (0.25 g, 2.19 mmol) was added slowly dropwise at ambient temperature to a stirred slurry of Rh-PFIEP[SO3H] (1.0 g, 0.387 mmol, prepared as described above), styrene (2.5 mL) and CH2Cl2 (2.5 mL). Gas evolution ceased about 1 hour after the addition of the ethyl diazoacetate solution was complete. The resulting slurry was stirred for 24 hours and then allowed to settle. The solution was removed, the resulting resin was washed with 3.0 mL of CH2Cl2. The solution and the wash were combined and analyzed for cyclopropane products. Yield (based on ethyl diazoacetate): 73.9%. The solution was removed the resulting resin was washed with 3.0 mL of CH2Cl2 Yield (based on ethyl diazoacetate)

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

Procedure: In Example 4, a flask was charged with 1.0 g of the catalyst described in Example 1, CH2Cl2 (2.5 mL), and styrene (2.5 mL). A solution of ethyl diazoacetate (0.23 g), CH2Cl2 (12.5 mL), and styrene (12.5 mL) was added slowly dropwise and the resulting mixture was stirred for 24 hours. The reaction product was analyzed by gas chromatography and the catalyst recovered by filtration. This process was repeated for a total of ten cycles during which yields of ethyl 2-phenylcyclopropane-carboxylate remained essentially constant at about 91%. The recovered catalyst was dried in vacuo. Duplicate elemental analyses gave copper contents of the recovered catalyst of 1.83 and 1.88%. the catalyst recovered by filtration

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

Procedure: In Example 4, a flask was charged with 1.0 g of the catalyst described in Example 1, CH2Cl2 (2.5 mL), and styrene (2.5 mL). A solution of ethyl diazoacetate (0.23 g), CH2Cl2 (12.5 mL), and styrene (12.5 mL) was added slowly dropwise and the resulting mixture was stirred for 24 hours. The reaction product was analyzed by gas chromatography and the catalyst recovered by filtration. This process was repeated for a total of ten cycles during which yields of ethyl 2-phenylcyclopropane-carboxylate remained essentially constant at about 91%. The recovered catalyst was dried in vacuo. Duplicate elemental analyses gave copper contents of the recovered catalyst of 1.83 and 1.88%. the catalyst recovered by filtration

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

Procedure: To a mixture of styrene (2.15g, 20.7 mmol) and Rh2 (4S-BNOX)4 (0.0113 g, 0.0131 mmol) in 5.0 mL of anhydrous dichloromethane was added, by syringe at room temperature, ethyl diazoacetate (0298 g, 2.62 mmol) in 3.0 mL of dichloromethane under nitrogen and at an addition rate of 0.8 mL/h (syringe pump). After addition was complete, the dichloromethane solution was passed through a plug of neutral alumina to separate the catalyst, and solvent and excess styrene were removed under reduced pressure Gas chromatographic separation of the trans-isomer produced a material whose specific rotation was -6.4° which corresponded to an enantiomeric excess of the ethyl (1R,2R)-2-phenylcyclopropanecarboxylate. Conversion of the ethyl esters to the 1-menthyl esters by base hydrolysis, acid chloride formation, and esterification with (-)-menthol provided a gas chromatographically separable mixture that showed 25% enantiomeric excess for the (1R,2R)-enantiomer of the trans-2-phenylcyclopropanecarboxylate. was added, by syringe at room temperature After addition to separate the catalyst, and solvent and excess styrene were removed under reduced pressure Gas chromatographic separation of the trans-isomer produced a material whose specific rotation was -6.4° provided a gas chromatographically separable mixture that

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

Procedure: To a mixture of styrene (2.15g, 20.7 mmol) and Rh2 (4S-BNOX)4 (0.0113 g, 0.0131 mmol) in 5.0 mL of anhydrous dichloromethane was added, by syringe at room temperature, ethyl diazoacetate (0298 g, 2.62 mmol) in 3.0 mL of dichloromethane under nitrogen and at an addition rate of 0.8 mL/h (syringe pump). After addition was complete, the dichloromethane solution was passed through a plug of neutral alumina to separate the catalyst, and solvent and excess styrene were removed under reduced pressure Gas chromatographic separation of the trans-isomer produced a material whose specific rotation was -6.4° which corresponded to an enantiomeric excess of the ethyl (1R,2R)-2-phenylcyclopropanecarboxylate. Conversion of the ethyl esters to the 1-menthyl esters by base hydrolysis, acid chloride formation, and esterification with (-)-menthol provided a gas chromatographically separable mixture that showed 25% enantiomeric excess for the (1R,2R)-enantiomer of the trans-2-phenylcyclopropanecarboxylate. was added, by syringe at room temperature After addition to separate the catalyst, and solvent and excess styrene were removed under reduced pressure Gas chromatographic separation of the trans-isomer produced a material whose specific rotation was -6.4° provided a gas chromatographically separable mixture that

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

Procedure: The reaction described in Example 3 was substantially repeated except that the Cu,K-PFIEP[SO3H] catalyst was replaced by the Cu,K-PFIEP[SO3H]/PFIEP[CO2H] (0.58 g) catalyst described above. The reaction mixture was allowed to stir for 0.5 hour after the addition of the solution of ethyl diazoacetate, CH2Cl2 and styrene. Analysis by gas chromatography showed that the combined yield of cis- and trans-ethyl-2-phenylcyclopropanecarboxylates was 95%.

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

Procedure: A solution of CH2Cl2 (12.5 mL), styrene (12 5 mL) and ethyl diazoacetate (0.25 g, 2.19 mmol) was added slowly dropwise at ambient temperature to a stirred slurry of Rh-PFIEP[SO3H] (1.0 g, 0.387 mmol, prepared as described above), styrene (2.5 mL) and CH2Cl2 (2.5 mL). Gas evolution ceased about 1 hour after the addition of the ethyl diazoacetate solution was complete. The resulting slurry was stirred for 24 hours and then allowed to settle. The solution was removed, the resulting resin was washed with 3.0 mL of CH2Cl2. The solution and the wash were combined and analyzed for cyclopropane products. Yield (based on ethyl diazoacetate): 73.9%. The solution was removed the resulting resin was washed with 3.0 mL of CH2Cl2 Yield (based on ethyl diazoacetate)

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

Procedure: In Example 4, a flask was charged with 1.0 g of the catalyst described in Example 1, CH2Cl2 (2.5 mL), and styrene (2.5 mL). A solution of ethyl diazoacetate (0.23 g), CH2Cl2 (12.5 mL), and styrene (12.5 mL) was added slowly dropwise and the resulting mixture was stirred for 24 hours. The reaction product was analyzed by gas chromatography and the catalyst recovered by filtration. This process was repeated for a total of ten cycles during which yields of ethyl 2-phenylcyclopropane-carboxylate remained essentially constant at about 91%. The recovered catalyst was dried in vacuo. Duplicate elemental analyses gave copper contents of the recovered catalyst of 1.83 and 1.88%. the catalyst recovered by filtration

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