ethyl 7-bromo-3-(3-hydroxypropyl)-1H-indole-2-carboxylate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of EXAMPLE 1B (1.116 g) in dichloromethane (30 mL) at 0° C. was added iodine (1.01 g), triphenyl phosphine (1.03 g) and imidazole (0.535 g). The mixture was stirred at 0° C. for 1 hour and treated with saturated NaHCO3 (50 mL). Stirring was continued for 30 minutes, and the organic layer was washed with a saturated aqueous Na2S2O3 (50 mL), water (20 mL), and brine (50 mL) and dried (Na2SO4), filtered and concentrated. The concentrate was purified by column chromatography on silica gel (with 0-20% ethyl acetate in hexanes. Stirring was continued for 30 minutes the organic layer was washed with a saturated aqueous Na2S2O3 (50 mL), water (20 mL), and brine (50 mL) dried (Na2SO4) filtered concentrated The concentrate was purified by column chromatography on silica gel (with 0-20% ethyl acetate in hexanes

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

実験手順: To a cooled (0° C.) mixture of EXAMPLE 1B (3.26 g) in dichloromethane (5 mL) was added DMSO (1 mL) and triethylamine (0.835 mL) followed by pyridine sulfate (636 mg). The mixture was stirred for 2 hours, diluted with ethyl acetate (150 mL), and washed with 5% HCl, saturated NaHCO3, water and brine and dried (Na2SO4), filtered and concentrated. washed with 5% HCl, saturated NaHCO3, water and brine dried (Na2SO4) filtered concentrated

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

実験手順: A mixture of EXAMPLE 1B (456 mg) and 2-methoxyphenylboronic acid (182.4 mg) in THF (10 mL), tris(dibenzylideneacetone)dipalladium(0) (46 mg), tri-tert-butylphosphine tetrafluoroborate (15 mg) and CsF (456 mg) was stirred at ambient temperature, diluted with ethyl acetate (200 mL), washed with water and brine, and dried (Na2SO4), filtered and concentrated. The concentrate was purified by flash column chromatography on silica gel with 20% ethyl acetate in hexanes. washed with water and brine dried (Na2SO4) filtered concentrated The concentrate was purified by flash column chromatography on silica gel with 20% ethyl acetate in hexanes

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

実験手順: To a mixture of Example 1B (10.87 g), 1-naphthol (5.77 g) and triphenylphosphine (10.5 g) in THF (100 mL) was added di-tert-butyl azodicarboxylate (9.21 g). The mixture was stirred for 3 days, concentrated, redissolved in dichloromethane, washed with water and brine and dried (MgSO4), filtered and concentrated. The concentrate was purified by flash column chromatography on silica gel with 0-10% ethyl acetate in hexanes. The product was recrystallized from hexanes. concentrated redissolved in dichloromethane washed with water and brine dried (MgSO4) filtered concentrated The concentrate was purified by flash column chromatography on silica gel with 0-10% ethyl acetate in hexanes The product was recrystallized from hexanes

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

実験手順: To a mixture of EXAMPLE 1A (1.85 g) in THF (50 mL) was added 1M borane.THF (30 mL). The mixture was stirred at room temperature for 16 hours, quenched with methanol (10 mL) and concentrated. The concentrate was purified by flash column chromatography on silica gel with 5-25% ethyl acetate/hexanes. quenched with methanol (10 mL) concentrated The concentrate was purified by flash column chromatography on silica gel with 5-25% ethyl acetate/hexanes

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

実験手順: To a mixture of EXAMPLE 1A (1.85 g) in THF (50 mL) was added 1M borane.THF (30 mL). The mixture was stirred at room temperature for 16 hours, quenched with methanol (10 mL) and concentrated. The concentrate was purified by flash column chromatography on silica gel with 5-25% ethyl acetate/hexanes. quenched with methanol (10 mL) concentrated The concentrate was purified by flash column chromatography on silica gel with 5-25% ethyl acetate/hexanes

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of EXAMPLE 1B (1.116 g) in dichloromethane (30 mL) at 0° C. was added iodine (1.01 g), triphenyl phosphine (1.03 g) and imidazole (0.535 g). The mixture was stirred at 0° C. for 1 hour and treated with saturated NaHCO3 (50 mL). Stirring was continued for 30 minutes, and the organic layer was washed with a saturated aqueous Na2S2O3 (50 mL), water (20 mL), and brine (50 mL) and dried (Na2SO4), filtered and concentrated. The concentrate was purified by column chromatography on silica gel (with 0-20% ethyl acetate in hexanes. Stirring was continued for 30 minutes the organic layer was washed with a saturated aqueous Na2S2O3 (50 mL), water (20 mL), and brine (50 mL) dried (Na2SO4) filtered concentrated The concentrate was purified by column chromatography on silica gel (with 0-20% ethyl acetate in hexanes

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

実験手順: To a cooled (0° C.) mixture of EXAMPLE 1B (3.26 g) in dichloromethane (5 mL) was added DMSO (1 mL) and triethylamine (0.835 mL) followed by pyridine sulfate (636 mg). The mixture was stirred for 2 hours, diluted with ethyl acetate (150 mL), and washed with 5% HCl, saturated NaHCO3, water and brine and dried (Na2SO4), filtered and concentrated. washed with 5% HCl, saturated NaHCO3, water and brine dried (Na2SO4) filtered concentrated

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

実験手順: A mixture of EXAMPLE 1B (456 mg) and 2-methoxyphenylboronic acid (182.4 mg) in THF (10 mL), tris(dibenzylideneacetone)dipalladium(0) (46 mg), tri-tert-butylphosphine tetrafluoroborate (15 mg) and CsF (456 mg) was stirred at ambient temperature, diluted with ethyl acetate (200 mL), washed with water and brine, and dried (Na2SO4), filtered and concentrated. The concentrate was purified by flash column chromatography on silica gel with 20% ethyl acetate in hexanes. washed with water and brine dried (Na2SO4) filtered concentrated The concentrate was purified by flash column chromatography on silica gel with 20% ethyl acetate in hexanes

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

実験手順: To a mixture of Example 1B (10.87 g), 1-naphthol (5.77 g) and triphenylphosphine (10.5 g) in THF (100 mL) was added di-tert-butyl azodicarboxylate (9.21 g). The mixture was stirred for 3 days, concentrated, redissolved in dichloromethane, washed with water and brine and dried (MgSO4), filtered and concentrated. The concentrate was purified by flash column chromatography on silica gel with 0-10% ethyl acetate in hexanes. The product was recrystallized from hexanes. concentrated redissolved in dichloromethane washed with water and brine dried (MgSO4) filtered concentrated The concentrate was purified by flash column chromatography on silica gel with 0-10% ethyl acetate in hexanes The product was recrystallized from hexanes

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

実験手順: To a mixture of EXAMPLE 1A (1.85 g) in THF (50 mL) was added 1M borane THF (30 mL). The mixture was stirred at room temperature for 16 hours, quenched with methanol (10 mL) and concentrated. The concentrate was purified by flash column chromatography on silica gel with 5-25% ethyl acetate/hexanes. quenched with methanol (10 mL) concentrated The concentrate was purified by flash column chromatography on silica gel with 5-25% ethyl acetate/hexanes

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of EXAMPLE 1B (1.116 g) in dichloromethane (30 mL) at 0° C. was added iodine (1.01 g), triphenyl phosphine (1.03 g) and imidazole (0.535 g). The mixture was stirred at 0° C. for 1 hour and treated with saturated NaHCO3 (50 mL). Stirring was continued for 30 minutes, and the organic layer was washed with a saturated aqueous Na2S2O3 (50 mL), water (20 mL), and brine (50 mL) and dried (Na2SO4), filtered and concentrated. The concentrate was purified by column chromatography on silica gel (with 0-20% ethyl acetate in hexanes. Stirring was continued for 30 minutes the organic layer was washed with a saturated aqueous Na2S2O3 (50 mL), water (20 mL), and brine (50 mL) dried (Na2SO4) filtered concentrated The concentrate was purified by column chromatography on silica gel (with 0-20% ethyl acetate in hexanes