2-bromoethynyl-tri(propan-2-yl)silane

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of t-butyl 4-morpholinobenzylcarbamate (1.11 g, 3.80 mmol), bromoethynyl-triisopropyl-silane, CuI (225 mg, 1.17 mmol) and 1,10-phenantroline (250 mg, 1.40 mmol) in dry toluene (7.5 ml) was warmed to 90° C. under a nitrogen atmosphere. KHMDS (10 ml, 0.5 M in toluene) was added dropwise under nitrogen atmosphere and the mixture was stirred for 12 hours at this temperature. The reaction mixture was cooled to RT; Et2O (30 ml) and NaCl/NH4OH (60/30 ml) were added and the organic phase was extracted with Et2O (3×30 ml), washed with NaCl/NH4 and dried over Na2SO4. The solvent was removed under reduced pressure to afford the title compound which was purified by column chromatography (PE/AcOEt:95/5). The reaction mixture was cooled to RT the organic phase was extracted with Et2O (3×30 ml) washed with NaCl/NH4 dried over Na2SO4 The solvent was removed under reduced pressure

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of t-butyl 4-morpholinobenzylcarbamate (1.11 g, 3.80 mmol), bromoethynyl-triisopropyl-silane, CuI (225 mg, 1.17 mmol) and 1,10-phenantroline (250 mg, 1.40 mmol) in dry toluene (7.5 ml) was warmed to 90° C. under a nitrogen atmosphere. KHMDS (10 ml, 0.5 M in toluene) was added dropwise under nitrogen atmosphere and the mixture was stirred for 12 hours at this temperature. The reaction mixture was cooled to RT; Et2O (30 ml) and NaCl/NH4OH (60/30 ml) were added and the organic phase was extracted with Et2O (3×30 ml), washed with NaCl/NH4 and dried over Na2SO4. The solvent was removed under reduced pressure to afford the title compound which was purified by column chromatography (PE/AcOEt:95/5). The reaction mixture was cooled to RT the organic phase was extracted with Et2O (3×30 ml) washed with NaCl/NH4 dried over Na2SO4 The solvent was removed under reduced pressure

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of t-butyl 4-morpholinophenylcarbamate (1.45 g, 7.60 mmol), bromoethynyl-triisopropyl-silane, CuI (450 mg, 2.34 mmol) and 1,10-phenantroline (500 mg, 2.80 mmol) in dry toluene (15 ml) was warmed up to 90° C. under a nitrogen atmosphere. KHMDS (20 ml, 0.5 M in toluene) was added dropwise under nitrogen and the mixture was stirred for 12 hours at this temperature. The reaction was cooled down to RT; Et2O (30 ml) and NaCl/NH4OH (60/30 ml) were added and the organic phase was extracted with Et2O (3×30 ml), washed with NaCl/NH4 and dried over Na2SO4. The solvent was removed under reduced pressure and the title compound was obtained after purification by column chromatography (PE/AcOEt: 95/5). The reaction was cooled down to RT the organic phase was extracted with Et2O (3×30 ml) washed with NaCl/NH4 dried over Na2SO4 The solvent was removed under reduced pressure

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of t-butyl 4-morpholinophenylcarbamate (1.45 g, 7.60 mmol), bromoethynyl-triisopropyl-silane, CuI (450 mg, 2.34 mmol) and 1,10-phenantroline (500 mg, 2.80 mmol) in dry toluene (15 ml) was warmed up to 90° C. under a nitrogen atmosphere. KHMDS (20 ml, 0.5 M in toluene) was added dropwise under nitrogen and the mixture was stirred for 12 hours at this temperature. The reaction was cooled down to RT; Et2O (30 ml) and NaCl/NH4OH (60/30 ml) were added and the organic phase was extracted with Et2O (3×30 ml), washed with NaCl/NH4 and dried over Na2SO4. The solvent was removed under reduced pressure and the title compound was obtained after purification by column chromatography (PE/AcOEt: 95/5). The reaction was cooled down to RT the organic phase was extracted with Et2O (3×30 ml) washed with NaCl/NH4 dried over Na2SO4 The solvent was removed under reduced pressure

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

Procedure: NBS (2.14 g, 12 mmol) and AgNO3 (170 mg, 1 mmol) were added to a solution of triisopropylsilylacetylene (2.24 ml, 10 mmol) in acetone (15 ml). The solution was stirred for 2 hours at RT. Pentane (20 ml) and H2O (20 ml) were added and the solution was stirred for 30 minutes. The organic phase was extracted with pentane (3×20 ml) and dried over Na2SO4. The solvent was removed under reduced pressure at RT and the residue was used in the next reaction without any purification. the solution was stirred for 30 minutes The organic phase was extracted with pentane (3×20 ml) dried over Na2SO4 The solvent was removed under reduced pressure at RT the residue was used in the next reaction without any purification

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

Procedure: NBS (2.14 g, 12 mmol) and AgNO3 (170 mg, 1 mmol) were added to a solution of triisopropylsilylacetylene (2.24 ml, 10 mmol) in acetone (15 ml). The solution was stirred for 2 hours at RT. Pentane (20 ml) and H2O (20 ml) were added and the solution was stirred for 30 minutes. The organic phase was extracted with pentane (3×20 ml) and dried over Na2SO4. The solvent was removed under reduced pressure at RT and the residue was used in the next reaction without any purification. the solution was stirred for 30 minutes The organic phase was extracted with pentane (3×20 ml) dried over Na2SO4 The solvent was removed under reduced pressure at RT the residue was used in the next reaction without any purification

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

Procedure: To a stirred solution of 8-chloro-2-methyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (10 g, 0.0454 mol) and copper sulfate (1.13 g, 0.00454 mol) in toluene (100 mL) was added potassium carbonate (12.5 g, 0.0909 mol) and 1,10 phenanthroline (1.6 g, 0.00909 mol). The reaction mixture was stirred for 5 min at RT. Bromoethynyl triisopropylsilane (13.0 g, 0.0499 mol) was added to the reaction mixture at the same temperature. After completion of addition, the reaction mixture was stirred overnight at 80° C., After completion of reaction (monitored by TLC), the mixture was cooled to RT, diluted with water (500 mL), and extracted with EtOAc (3×500 mL). The organic layer was dried over anhydrous sodium sulfate and solvent was removed under pressure. The product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch) to provide the desired compound as a dark brown colored oil (8.0 g, 44% yield). After completion of addition the reaction mixture was stirred overnight at 80° C. After completion of reaction (monitored by TLC) the mixture was cooled to RT extracted with EtOAc (3×500 mL) The organic layer was dried over anhydrous sodium sulfate and solvent was removed under pressure The product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch)

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

Procedure: To a stirred solution of 2,8-dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (10 g, 0.05 mol) and copper sulfate (1.24 g, 0.005 mol) in toluene (200 mL) was added potassium carbonate (13.8 g, 0.1 mol) and 1,10 phenanthroline (1.8 g, 0.01 mol). The reaction mixture was stirred for 5 min at RT. (Bromoethynyl)triisopropylsilane (14.4 g, 0.055 mol) was added to the reaction mixture at the same temperature. After completion of addition, the reaction mixture was stirred overnight at 80° C. The reaction was monitored by TLC. After completion of reaction, the mixture was cooled to RT, diluted with water (500 mL), and extracted with EtOAc (3×500 mL). The organic layer was dried over anhydrous sodium sulfate and solvent was removed under reduced pressure. The crude product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch) to provide the desired compound as a dark brown colored oil (9.5 g, 50% yield). After completion of addition the reaction mixture was stirred overnight at 80° C After completion of reaction the mixture was cooled to RT extracted with EtOAc (3×500 mL) The organic layer was dried over anhydrous sodium sulfate and solvent was removed under reduced pressure The crude product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch)

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

Procedure: To a stirred solution of 8-chloro-2-methyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (10 g, 0.0454 mol) and copper sulfate (1.13 g, 0.00454 mol) in toluene (100 mL) was added potassium carbonate (12.5 g, 0.0909 mol) and 1,10 phenanthroline (1.6 g, 0.00909 mol). The reaction mixture was stirred for 5 min at RT. Bromoethynyl triisopropylsilane (13.0 g, 0.0499 mol) was added to the reaction mixture at the same temperature. After completion of addition, the reaction mixture was stirred overnight at 80° C. After completion of reaction (monitored by TLC), the mixture was cooled to RT, diluted with water (500 mL), and extracted with EtOAc (3×500 mL). The organic layer was dried over anhydrous sodium sulfate and solvent was removed under pressure. The product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch) to provide the desired compound as a dark brown colored oil (8.0 g, 44% yield). After completion of addition the reaction mixture was stirred overnight at 80° C After completion of reaction (monitored by TLC) the mixture was cooled to RT extracted with EtOAc (3×500 mL) The organic layer was dried over anhydrous sodium sulfate and solvent was removed under pressure The product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch)

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

Procedure: To a stirred solution of 2,8-dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (10 g, 0.05 mol) and copper sulfate (1.24 g, 0.005 mol) in toluene (200 mL) was added potassium carbonate (13.8 g, 0.1 mol) and 1,10 phenanthroline (1.8 g, 0.01 mol). The reaction mixture was stirred for 5 min at RT. (Bromoethynyl) triisopropylsilane (14.4 g, 0.055 mol) was added to the reaction mixture at the same temperature. After completion of addition, the reaction mixture was stirred overnight at 80° C. The reaction was monitored by TLC. After completion of reaction, the mixture was cooled to RT, diluted with water (500 mL), and extracted with EtOAc (3×500 mL). The organic layer was dried over anhydrous sodium sulfate and solvent was removed under reduced pressure. The crude product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch) to provide the desired compound as a dark brown colored oil (9.5 g, 50% yield). After completion of addition the reaction mixture was stirred overnight at 80° C After completion of reaction the mixture was cooled to RT extracted with EtOAc (3×500 mL) The organic layer was dried over anhydrous sodium sulfate and solvent was removed under reduced pressure The crude product was purified by column chromatography (1% MeOH:DCM in silica 100-200 mesh, diameter of column—5 cm, height of silica—approx. 5 inch)

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of t-butyl 4-morpholinobenzylcarbamate (1.11 g, 3.80 mmol), bromoethynyl-triisopropyl-silane, CuI (225 mg, 1.17 mmol) and 1,10-phenantroline (250 mg, 1.40 mmol) in dry toluene (7.5 ml) was warmed to 90° C. under a nitrogen atmosphere. KHMDS (10 ml, 0.5 M in toluene) was added dropwise under nitrogen atmosphere and the mixture was stirred for 12 hours at this temperature. The reaction mixture was cooled to RT; Et2O (30 ml) and NaCl/NH4OH (60/30 ml) were added and the organic phase was extracted with Et2O (3×30 ml), washed with NaCl/NH4 and dried over Na2SO4. The solvent was removed under reduced pressure to afford the title compound which was purified by column chromatography (PE/AcOEt:95/5). The reaction mixture was cooled to RT the organic phase was extracted with Et2O (3×30 ml) washed with NaCl/NH4 dried over Na2SO4 The solvent was removed under reduced pressure

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of t-butyl 4-morpholinophenylcarbamate (1.45 g, 7.60 mmol), bromoethynyl-triisopropyl-silane, CuI (450 mg, 2.34 mmol) and 1,10-phenantroline (500 mg, 2.80 mmol) in dry toluene (15 ml) was warmed up to 90° C. under a nitrogen atmosphere. KHMDS (20 ml, 0.5 M in toluene) was added dropwise under nitrogen and the mixture was stirred for 12 hours at this temperature. The reaction was cooled down to RT; Et2O (30 ml) and NaCl/NH4OH (60/30 ml) were added and the organic phase was extracted with Et2O (3×30 ml), washed with NaCl/NH4 and dried over Na2SO4. The solvent was removed under reduced pressure and the title compound was obtained after purification by column chromatography (PE/AcOEt: 95/5). The reaction was cooled down to RT the organic phase was extracted with Et2O (3×30 ml) washed with NaCl/NH4 dried over Na2SO4 The solvent was removed under reduced pressure