1H-Indole, 4-broMo-5-Methoxy-

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

Procedure: 7-Bromo-5-methoxy-1H-indole CLXXVIII was prepared from 3-bromo-4-nitro-anisole using the procedure described for preparation of 4-bromo-5-methoxyindole XLVI (Example 12).

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

Procedure: 7-Bromo-5-methoxy-1H-indole CLXXVIII was prepared from 3-bromo-4-nitro-anisole using the procedure described for preparation of 4-bromo-5-methoxyindole XLVI (Example 12).

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

Procedure: 6-Bromo-7-methoxy-1H-indole CXXXVII (14% yield) was prepared from 2-bromo-6-nitro-anisole using the procedure described above for preparation of 4-bromo-5-methoxyindole XLVI (Example 12).

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

Procedure: 6-Bromo-7-methoxy-1H-indole CXXXVII (14% yield) was prepared from 2-bromo-6-nitro-anisole using the procedure described above for preparation of 4-bromo-5-methoxyindole XLVI (Example 12).

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

Procedure: To a −40° C. solution of 2-bromo-4-nitro-anisole (1.16 g, 5 mmol) in THF (10 ml) was added vinylmagnesium bromide (1M in THF, 15 ml). The reaction mixture was stirred for 30 min while allowing the temperature to rise to −20° C. The reaction was quenched by addition of a saturated solution of NH4Cl, diluted with Et2O, and the aqueous layer was extracted twice with Et2O. The combined organic layers were dried over Na2SO4, filtered, concentrated, and purified via flash chromatography (hexane/EtOAc) to provide 4-bromo-5-methoxyindole XLVI (38 mg, 3% yield) as an oil. to rise to −20° C The reaction was quenched by addition of a saturated solution of NH4Cl diluted with Et2O the aqueous layer was extracted twice with Et2O The combined organic layers were dried over Na2SO4 filtered concentrated purified via flash chromatography (hexane/EtOAc)

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

Procedure: To a −40° C. solution of 2-bromo-4-nitro-anisole (1.16 g, 5 mmol) in THF (10 ml) was added vinylmagnesium bromide (1M in THF, 15 ml). The reaction mixture was stirred for 30 min while allowing the temperature to rise to −20° C. The reaction was quenched by addition of a saturated solution of NH4Cl, diluted with Et2O, and the aqueous layer was extracted twice with Et2O. The combined organic layers were dried over Na2SO4, filtered, concentrated, and purified via flash chromatography (hexane/EtOAc) to provide 4-bromo-5-methoxyindole XLVI (38 mg, 3% yield) as an oil. to rise to −20° C The reaction was quenched by addition of a saturated solution of NH4Cl diluted with Et2O the aqueous layer was extracted twice with Et2O The combined organic layers were dried over Na2SO4 filtered concentrated purified via flash chromatography (hexane/EtOAc)

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

Procedure: A solution of 4-bromo-5-methoxyindole (540 mg, 2.4 mmol) in dichloromethane (12 ml) was cooled to −40° C. under an atmosphere of nitrogen. Boron tribromide (4.8 ml of a 1M solution in dichloromethane, 4.8 mmol) was added dropwise then the mixture warmed to ambient temperature and stirred for 1 hour. The mixture was diluted with dichloromethane (5 ml) and washed with 2M aqueous hydrochloric acid (3 ml). The organic layer was separated, dried (MgSO4) and evaporated to give a dark oil. This was purified by silica column chromatography eluting with dichloromethane/ethyl acetate (8/2) to give 4-bromo-5-hydroxyindole (295 mg, 55%). washed with 2M aqueous hydrochloric acid (3 ml) The organic layer was separated dried (MgSO4) evaporated to give a dark oil This was purified by silica column chromatography eluting with dichloromethane/ethyl acetate (8/2)

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

Procedure: A solution of 4-bromo-5-methoxyindole (540 mg, 2.4 mmol) in dichloromethane (12 ml) was cooled to −40° C. under an atmosphere of nitrogen. Boron tribromide (4.8 ml of a 1M solution in dichloromethane, 4.8 mmol) was added dropwise then the mixture warmed to ambient temperature and stirred for 1 hour. The mixture was diluted with dichloromethane (5 ml) and washed with 2M aqueous hydrochloric acid (3 ml). The organic layer was separated, dried (MgSO4) and evaporated to give a dark oil. This was purified by silica column chromatography eluting with dichloromethane/ethyl acetate (8/2) to give 4-bromo-5-hydroxyindole (295 mg, 55%). washed with 2M aqueous hydrochloric acid (3 ml) The organic layer was separated dried (MgSO4) evaporated to give a dark oil This was purified by silica column chromatography eluting with dichloromethane/ethyl acetate (8/2)

Conditions: temp:245.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-5-methoxyindole-2-carboxylic acid (1.25 g, 4.19 mmol), quinoline (15 ml) and copper chromite (313 mg) were mixed together. Nitrogen was gently bubbled through the mixture for 5 minutes, then the mixture heated quickly to 245° C. under an atmosphere of nitrogen. After 90 minutes the mixture was cooled to ambient temperature diluted with ethyl acetate (100 ml) and washed with 2M aqueous hydrochloric acid (60 ml). The ethyl acetate layer was filtered, the filtrate dried (MgSO4) and the solvent evaporated. The residue was purified by silica column chromatography eluting with dichloromethane/hexane (1/1) to give 4-bromo-5-methoxyindole (635 mg, 60%). Nitrogen was gently bubbled through the mixture for 5 minutes After 90 minutes the mixture was cooled to ambient temperature diluted with ethyl acetate (100 ml) washed with 2M aqueous hydrochloric acid (60 ml) The ethyl acetate layer was filtered the filtrate dried (MgSO4) the solvent evaporated The residue was purified by silica column chromatography eluting with dichloromethane/hexane (1/1)

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

Procedure: 7-Bromo-5-methoxy-1H-indole CLXXVIII was prepared from 3-bromo-4-nitro-anisole using the procedure described for preparation of 4-bromo-5-methoxyindole XLVI (Example 12).

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

Procedure: 6-Bromo-7-methoxy-1H-indole CXXXVII (14% yield) was prepared from 2-bromo-6-nitro-anisole using the procedure described above for preparation of 4-bromo-5-methoxyindole XLVI (Example 12).

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

Procedure: To a −40° C. solution of 2-bromo-4-nitro-anisole (1.16 g, 5 mmol) in THF (10 ml) was added vinylmagnesium bromide (1M in THF, 15 ml). The reaction mixture was stirred for 30 min while allowing the temperature to rise to −20° C. The reaction was quenched by addition of a saturated solution of NH4Cl, diluted with Et2O, and the aqueous layer was extracted twice with Et2O. The combined organic layers were dried over Na2SO4, filtered, concentrated, and purified via flash chromatography (hexane/EtOAc) to provide 4-bromo-5-methoxyindole XLVI (38 mg, 3% yield) as an oil. to rise to −20° C The reaction was quenched by addition of a saturated solution of NH4Cl diluted with Et2O the aqueous layer was extracted twice with Et2O The combined organic layers were dried over Na2SO4 filtered concentrated purified via flash chromatography (hexane/EtOAc)