dicyclopropylmethanol

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of dicyclopropylmethan-1-ol (1.5 mL, 12.7 mmol) in dichloromethane (20 mL) is added rhodium (II) acetate dimer (10 mg) followed by ethyl diazoacetate (1.26 mL, 12.0 mmol). The reaction mixture is stirred at rt for 48 h. The reaction mixture is diluted with heptane, and filtered. The filtrate is evaporated, and the residue is vacuum distilled at 170° C. to give 1.24 g of the product 448. filtered The filtrate is evaporated distilled at 170° C.

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of dicyclopropylmethan-1-ol (1.5 mL, 12.7 mmol) in dichloromethane (20 mL) is added rhodium (II) acetate dimer (10 mg) followed by ethyl diazoacetate (1.26 mL, 12.0 mmol). The reaction mixture is stirred at rt for 48 h. The reaction mixture is diluted with heptane, and filtered. The filtrate is evaporated, and the residue is vacuum distilled at 170° C. to give 1.24 g of the product 448. filtered The filtrate is evaporated distilled at 170° C.

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

実験手順: To a solution of dicyclopropylmethan-1-ol (1.5 mL, 12.7 mmol) in dichloromethane (20 mL) is added rhodium (II) acetate dimer (10 mg) followed by ethyl diazoacetate (1.26 mL, 12.0 mmol). The reaction mixture is stirred at rt for 48 h. The reaction mixture is diluted with heptane, and filtered. The filtrate is evaporated, and the residue is vacuum distilled at 170° C. to give 1.24 g of the product 448. filtered The filtrate is evaporated distilled at 170° C.

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

実験手順: To a solution of 4.48 g of dicyclopropylmethyl alcohol in 20 mL of CH2Cl2 was added 3.6 g of NaN3 followed by 10 g of CCl3CO2H. The resulting mixture was stirred at room temperature for 3 h, diluted with 50 mL of CH2Cl2, washed with NaHCO3 and NaCl solution. Drying over MgSO4 and removal of solvent gave an oil (which was examined by high field 1H NMR and shown to be contaminated by a small amount of ring-opening compound (less than 5%)) which was dissolved in a solution of 7 mL of toluene containing 2.5 g of hexadecyltributyl phosphonium bromide. To the solution was added 5 g of NaBH4 in 15 mL of H2O through a dropping funnel over 30 min. The mixture was stirred at 80° C. for 16 h, layers separated and the organic layer extracted with 10 % HCl. The pH of the aqueous solution was adjusted to 8-9 with NaOH and extracted with ether. After drying over MgSO4, HCl gas was bubbled through the solution and the amine hydrochloride salt which had precipitated was collected by filtration and recrystallized from ether/MeOH to give 1.8 g (35%) of the salt as white crystals, mp 250° C. dec. washed with NaHCO3 and NaCl solution Drying over MgSO4 and removal of solvent gave an oil (which The mixture was stirred at 80° C. for 16 h layers separated the organic layer extracted with 10 % HCl extracted with ether After drying over MgSO4, HCl gas was bubbled through the solution the amine hydrochloride salt which had precipitated was collected by filtration recrystallized from ether/MeOH

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

実験手順: To a solution of 4-nitro-1H-pyrazole (500 mg), dicyclopropylmethanol (0.92 g) and triphenylphosphine (2.3 g) in THF (10 mL) was added diisopropyl azodicarboxylate toluene (1.9M, 4.6 mL) solution at room temperature. The reaction mixture was stirred at room temperature for 2 hr, water was added thereto, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. A suspension of the obtained residue and palladium on carbon (1 g) in methanol (30 mL) was stirred at room temperature for 12 hr under a hydrogen atmosphere, filtered, and concentrated under reduced pressure. The residue was purified by preparative HPLC to give the title compound (140 mg). the mixture was extracted with ethyl acetate The extract was dried over anhydrous magnesium sulfate concentrated under reduced pressure A suspension of the obtained residue and palladium on carbon (1 g) in methanol (30 mL) was stirred at room temperature for 12 hr under a hydrogen atmosphere filtered concentrated under reduced pressure The residue was purified by preparative HPLC

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

実験手順: Dicyclopropylmethanol (880 mg) obtained in Step 1 and (R)-glycidyl nosylate (3.05 g) were dissolved in tetrahydrofuran (7.3 ml), sodium hydride (471 mg) and dimethyl sulfoxide (1.5 ml) were added under ice-cooling, and the mixture was stirred at room temperature for 5 hr. Water was poured into the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed successively with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=90:10) to give the title compound (760 mg). cooling the mixture was extracted with diethyl ether The organic layer was washed successively with water and brine dried over anhydrous sodium sulfate concentrated under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=90:10)

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

実験手順: To a solution of dicyclopropylmethan-1-ol (1.5 mL, 12.7 mmol) in dichloromethane (20 mL) is added rhodium (II) acetate dimer (10 mg) followed by ethyl diazoacetate (1.26 mL, 12.0 mmol). The reaction mixture is stirred at rt for 48 h. The reaction mixture is diluted with heptane, and filtered. The filtrate is evaporated, and the residue is vacuum distilled at 170° C. to give 1.24 g of the product 448. filtered The filtrate is evaporated distilled at 170° C.