ethenylcyclopentane

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

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

Procedure: 9-Borabicyclo[3,3,1]nonane (9-BBN) (tetrahydrofuran solution, 0.5 mol/L, 33 mL, 16.5 mmol) was added dropwise to a solution of vinylcyclopentane (1.59 g, 16.5 mmol) in tetrahydrofuran (7.5 mL) at 0° C. under a nitrogen atomosphere. The mixture was warmed gradually to room temperature and stirred for 15 hr. To the reaction mixture were added dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) (367 mg, 0.45 mmol), 4-bromo-2-fluoroaniline (2.85 g, 15.0 mmol) and 3 mol/L aqueous sodium hydroxide solution (15 mL, 45.0 mmol), and the mixture was heated to reflux for 10 hr. After cooling, ethyl acetate was added thereto, the mixture was filtered through Celite (registered trademark), and the filtrate was concentrated under reduced pressure. Water was added thereto, the mixture was extracted with ethyl acetate, and the organic layer was washed with brine. After drying over anhydrous magnesium sulfate, the desiccant was filtered off, followed by concentration under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1) to afford the title compound as a pale yellow oil (3.01 g). the mixture was heated to reflux for 10 hr After cooling the mixture was filtered through Celite (registered trademark) the filtrate was concentrated under reduced pressure Water was added the mixture was extracted with ethyl acetate the organic layer was washed with brine After drying over anhydrous magnesium sulfate the desiccant was filtered off followed by concentration under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)

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

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

Procedure: Prepared using 5-bromo-3-methyl-1-(2-methylpropyl)-6-[[2-(trifluoromethyl)phenyl]methyl]-thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione and cyclopentyl-ethene. The crude product was purified by flash silica chromatography eluting with a gradient of 5-20% ethanol in dichloromethane to give the title compound as a yellow oil (0.17 g). Prepared The crude product was purified by flash silica chromatography eluting with a gradient of 5-20% ethanol in dichloromethane

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

Procedure: 550 mg of 51 (2.47 mmol), 0.987 g of vinylcyclopentane (10.26 mmol), 18 mL of CH2Cl2 and 63 mg of 2nd generation Grubb's catalyst (C46H65Cl2N2PRu, MW 848.98, 0.030 mmol) are added to a 50 mL round-bottomed flask. The medium is stirred for 24 h at RT and then the insoluble material is filtered and the solvent is evaporated. The crude product is chromatographed on a silica cartridge (40 g, eluent AcOEt/heptane—in an AcOEt gradient: 50 to 100%). 85 mg of expected product 52 are obtained. the insoluble material is filtered the solvent is evaporated The crude product is chromatographed on a silica cartridge (40 g, eluent AcOEt/heptane—in an AcOEt gradient

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

Procedure: 2 g of 31 (10.63 mmol), 4.22 g of vinylcyclopentane (43.92 mmol), 80 mL of CH2Cl2 and 226 mg of 2nd generation Grubb's catalyst (C46H65Cl2N2PRu, MW 848.98, 0.266 mmol) are added to a 250 mL round-bottomed flask. The medium is stirred for 2 h at RT and then heated for 4 h at 45° C. The insoluble material is filtered and then the solvent is evaporated and the crude product (3.39 g) is chromatographed on a silica cartridge (150 g), eluting with a heptane/AcOEt (50/50) mixture. 1.39 g of expected product 32 (white solid) are obtained. heated for 4 h at 45° C The insoluble material is filtered the solvent is evaporated the crude product (3.39 g) is chromatographed on a silica cartridge (150 g) eluting with a heptane/AcOEt (50/50) mixture

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 100 mg (0.53 mmol) of 18, 4 ml of CH2Cl2, 726 μl (5.3 mmol) of vinylcyclopentane and then 90.2 mg (106 μmol) of second-generation Grubbs catalyst are introduced into a 5 ml vial. The solution is microwave-heated at 60° C. for 10 min. The solvent is subsequently evaporated to dryness under reduced pressure and the residue is then purified on a Biotage 12-M silica column (eluent: 40/60 Hept/EtOAc). The product 19 (76.3 mg, Rf=0.35 under the elution conditions used) is obtained in the form of a brown solid. The solvent is subsequently evaporated to dryness under reduced pressure the residue is then purified on a Biotage 12-M silica column (eluent: 40/60 Hept/EtOAc) The product 19 (76.3 mg, Rf=0.35 under the elution conditions is obtained in the form of a brown solid

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

Procedure: 9-Borabicyclo[3,3,1]nonane (9-BBN) (tetrahydrofuran solution, 0.5 mol/L, 33 mL, 16.5 mmol) was added dropwise to a solution of vinylcyclopentane (1.59 g, 16.5 mmol) in tetrahydrofuran (7.5 mL) at 0° C. under a nitrogen atomosphere. The mixture was warmed gradually to room temperature and stirred for 15 hr. To the reaction mixture were added dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) (367 mg, 0.45 mmol), 4-bromo-2-fluoroaniline (2.85 g, 15.0 mmol) and 3 mol/L aqueous sodium hydroxide solution (15 mL, 45.0 mmol), and the mixture was heated to reflux for 10 hr. After cooling, ethyl acetate was added thereto, the mixture was filtered through Celite (registered trademark), and the filtrate was concentrated under reduced pressure. Water was added thereto, the mixture was extracted with ethyl acetate, and the organic layer was washed with brine. After drying over anhydrous magnesium sulfate, the desiccant was filtered off, followed by concentration under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1) to afford the title compound as a pale yellow oil (3.01 g). the mixture was heated to reflux for 10 hr After cooling the mixture was filtered through Celite (registered trademark) the filtrate was concentrated under reduced pressure Water was added the mixture was extracted with ethyl acetate the organic layer was washed with brine After drying over anhydrous magnesium sulfate the desiccant was filtered off followed by concentration under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)