2-[(2-methylpropan-2-yl)oxy]benzaldehyde

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

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

Procedure: N-Boc-ethylenediamine (2.6 g, 16 mmol) and 8 (2.9 g, 16 mmol) were added to 250 mL of CH3CN and the reaction mixture was refluxed under argon for 4 hr. After cooling down to room temperature, the solvent was removed and the residue was redissolved in MeOH. The solvent was then evaporated and NaBH4 (3 g, 16 mmol) was added and stirred overnight. The solvent was evaporated, followed by extraction with CH2Cl2. The CH2Cl2 extract was concentrated and purified by a silica gel column using 2% methanolic NH3 (7 M NH3 in methanol/98% CH2Cl2 as eluent to yield the desired product as a pale yellow oil (97%). 1H NMR (CDCl3) δ 7.204 (dd, 1H, Ar), 7.115 (ddd, 1H, Ar), 7.007 (dd, 1H, Ar), 6.930 (ddd, 1H, Ar), 3.718 (s, 2H, —CH2—), 3.175 (d, 2H, —CH2—), 2.638 (t, 2H, —CH2—), 1.402 (s, 9H, —C(CH3)3), 1.382 (s, 9H, —C(CH3)3). Mass Spect.=323.23 (M+H)+. the reaction mixture was refluxed under argon for 4 hr the solvent was removed the residue was redissolved in MeOH The solvent was then evaporated The solvent was evaporated followed by extraction with CH2Cl2 The CH2Cl2 extract was concentrated purified by a silica gel column

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

Procedure: 2-(Aminomethyl)pyridine (0.849 g, 7.85 mmol) and 8 (1.4 g, 7.8 mmol) were added to 150 mL of CH3CN and the reaction mixture was refluxed under argon for 4 hr. After cooling down to room temperature, the solvent was removed and the residue was redissolved in MeOH. The solvent was then evaporated and NaBH4 (1.485 g, 39 mmol) was added and stirred overnight. The solvent was evaporated, followed by extraction with CH2Cl2. The CH2Cl2 extract was concentrated and purified by a silica gel column using 3% methanolic NH3 (7 M NH3 in methanol/97% CH2Cl2 as eluent to yield the desired product as a pale yellow oil (58%). 1H NMR (CDCl3) δ 8.530 (m, 1H, Ar), 7.604 (ddd, 1H, Ar), 7.330 (m, 2H, Ar), 7.128 (m, 2H, Ar), 7.027 (d, 2H, Ar), 6.969 (ddd, 1H, Ar), 3.892 (s, 2H, —CH2—), 3.837 (s, 2H, —CH2—), 2.523 (s, 1H, —CH—), 1.373 (s, 9H, —C(CH3)3). Mass Spec.=271.18 (M+H)+. the reaction mixture was refluxed under argon for 4 hr the solvent was removed the residue was redissolved in MeOH The solvent was then evaporated The solvent was evaporated followed by extraction with CH2Cl2 The CH2Cl2 extract was concentrated purified by a silica gel column

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

Procedure: To a stirred solution of 7 (3.8 g, 21 mmol) in 250 mL CH2Cl2, MnO2 (11 g, 126 mmol) was added. The reaction mixture was stirred overnight, filtered on Celite® and the solvent was distilled under reduced pressure. The crude product was purified by a silica gel column with 17% EtOAc/83% Hexane as eluents. The product was isolated as pale yellow oil (70% yield). 1H NMR (CDCl3) δ 7.286 (dd, 1H, Ar), 7.195 (ddd, 1H, Ar), 7.063 (d, 1H, Ar), 7.003 (ddd, 1H, Ar), 4.669 (s, 2H, —CH2—), 1.447 (s, 9H, —C(CH3)3). Mass Spec.=203.09 (M+H)++Na+. filtered on Celite® the solvent was distilled under reduced pressure The crude product was purified by a silica gel column with 17% EtOAc/83% Hexane as eluents

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

Procedure: 2-tert-Butoxybenzaldehyde (550 mg, 3.09 mmol) was treated with nitromethane (1167 μL, 21.6 mmol) at ambient temperature in a flask. Solid methylamine hydrochloride (133 mg, 1.98 mmol) and sodium acetate (162 mg, 1.98 mmol) were added and the colorless reaction mixture was stirred rapidly at ambient temperature. After 30 minutes, the reaction mixture started to turn yellow. After 16 hours, the reaction was very yellow and precipitate has formed. Water (20 ml) and dichloromethane (40 ml) were added and the layers partitioned. The dichloromethane layer was dried with sodium sulfate, filtered, and concentrated to provide the title compound (705 mg, 3.19 mmol, 103% yield) as a yellow oil. After 16 hours precipitate has formed the layers partitioned The dichloromethane layer was dried with sodium sulfate filtered concentrated

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

Procedure: 2-tert-Butoxybenzaldehyde (550 mg, 3.09 mmol) was treated with nitromethane (1167 μL, 21.6 mmol) at ambient temperature in a flask. Solid methylamine hydrochloride (133 mg, 1.98 mmol) and sodium acetate (162 mg, 1.98 mmol) were added and the colorless reaction mixture was stirred rapidly at ambient temperature. After 30 minutes, the reaction mixture started to turn yellow. After 16 hours, the reaction was very yellow and precipitate has formed. Water (20 ml) and dichloromethane (40 ml) were added and the layers partitioned. The dichloromethane layer was dried with sodium sulfate, filtered, and concentrated to provide the title compound (705 mg, 3.19 mmol, 103% yield) as a yellow oil. After 16 hours precipitate has formed the layers partitioned The dichloromethane layer was dried with sodium sulfate filtered concentrated

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

Procedure: 2-tert-Butoxybenzaldehyde (550 mg, 3.09 mmol) was treated with nitromethane (1167 μL, 21.6 mmol) at ambient temperature in a flask. Solid methylamine hydrochloride (133 mg, 1.98 mmol) and sodium acetate (162 mg, 1.98 mmol) were added and the colorless reaction mixture was stirred rapidly at ambient temperature. After 30 minutes, the reaction mixture started to turn yellow. After 16 hours, the reaction was very yellow and precipitate has formed. Water (20 ml) and dichloromethane (40 ml) were added and the layers partitioned. The dichloromethane layer was dried with sodium sulfate, filtered, and concentrated to provide the title compound (705 mg, 3.19 mmol, 103% yield) as a yellow oil. After 16 hours precipitate has formed the layers partitioned The dichloromethane layer was dried with sodium sulfate filtered concentrated

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

Procedure: N-Boc-ethylenediamine (2.6 g, 16 mmol) and 8 (2.9 g, 16 mmol) were added to 250 mL of CH3CN and the reaction mixture was refluxed under argon for 4 hr. After cooling down to room temperature, the solvent was removed and the residue was redissolved in MeOH. The solvent was then evaporated and NaBH4 (3 g, 16 mmol) was added and stirred overnight. The solvent was evaporated, followed by extraction with CH2Cl2. The CH2Cl2 extract was concentrated and purified by a silica gel column using 2% methanolic NH3 (7 M NH3 in methanol/98% CH2Cl2 as eluent to yield the desired product as a pale yellow oil (97%). 1H NMR (CDCl3) δ 7.204 (dd, 1H, Ar), 7.115 (ddd, 1H, Ar), 7.007 (dd, 1H, Ar), 6.930 (ddd, 1H, Ar), 3.718 (s, 2H, —CH2—), 3.175 (d, 2H, —CH2—), 2.638 (t, 2H, —CH2—), 1.402 (s, 9H, —C(CH3)3), 1.382 (s, 9H, —C(CH3)3). Mass Spect.=323.23 (M+H)+. the reaction mixture was refluxed under argon for 4 hr the solvent was removed the residue was redissolved in MeOH The solvent was then evaporated The solvent was evaporated followed by extraction with CH2Cl2 The CH2Cl2 extract was concentrated purified by a silica gel column

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

Procedure: N-Boc-ethylenediamine (2.6 g, 16 mmol) and 8 (2.9 g, 16 mmol) were added to 250 mL of CH3CN and the reaction mixture was refluxed under argon for 4 hr. After cooling down to room temperature, the solvent was removed and the residue was redissolved in MeOH. The solvent was then evaporated and NaBH4 (3 g, 16 mmol) was added and stirred overnight. The solvent was evaporated, followed by extraction with CH2Cl2. The CH2Cl2 extract was concentrated and purified by a silica gel column using 2% methanolic NH3 (7 M NH3 in methanol/98% CH2Cl2 as eluent to yield the desired product as a pale yellow oil (97%). 1H NMR (CDCl3) δ 7.204 (dd, 1H, Ar), 7.115 (ddd, 1H, Ar), 7.007 (dd, 1H, Ar), 6.930 (ddd, 1H, Ar), 3.718 (s, 2H, —CH2—), 3.175 (d, 2H, —CH2—), 2.638 (t, 2H, —CH2—), 1.402 (s, 9H, —C(CH3)3), 1.382 (s, 9H, —C(CH3)3). Mass Spect.=323.23 (M+H)+. the reaction mixture was refluxed under argon for 4 hr the solvent was removed the residue was redissolved in MeOH The solvent was then evaporated The solvent was evaporated followed by extraction with CH2Cl2 The CH2Cl2 extract was concentrated purified by a silica gel column

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

Procedure: 2-(Aminomethyl)pyridine (0.849 g, 7.85 mmol) and 8 (1.4 g, 7.8 mmol) were added to 150 mL of CH3CN and the reaction mixture was refluxed under argon for 4 hr. After cooling down to room temperature, the solvent was removed and the residue was redissolved in MeOH. The solvent was then evaporated and NaBH4 (1.485 g, 39 mmol) was added and stirred overnight. The solvent was evaporated, followed by extraction with CH2Cl2. The CH2Cl2 extract was concentrated and purified by a silica gel column using 3% methanolic NH3 (7 M NH3 in methanol/97% CH2Cl2 as eluent to yield the desired product as a pale yellow oil (58%). 1H NMR (CDCl3) δ 8.530 (m, 1H, Ar), 7.604 (ddd, 1H, Ar), 7.330 (m, 2H, Ar), 7.128 (m, 2H, Ar), 7.027 (d, 2H, Ar), 6.969 (ddd, 1H, Ar), 3.892 (s, 2H, —CH2—), 3.837 (s, 2H, —CH2—), 2.523 (s, 1H, —CH—), 1.373 (s, 9H, —C(CH3)3). Mass Spec.=271.18 (M+H)+. the reaction mixture was refluxed under argon for 4 hr the solvent was removed the residue was redissolved in MeOH The solvent was then evaporated The solvent was evaporated followed by extraction with CH2Cl2 The CH2Cl2 extract was concentrated purified by a silica gel column

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

Procedure: 2-(Aminomethyl)pyridine (0.849 g, 7.85 mmol) and 8 (1.4 g, 7.8 mmol) were added to 150 mL of CH3CN and the reaction mixture was refluxed under argon for 4 hr. After cooling down to room temperature, the solvent was removed and the residue was redissolved in MeOH. The solvent was then evaporated and NaBH4 (1.485 g, 39 mmol) was added and stirred overnight. The solvent was evaporated, followed by extraction with CH2Cl2. The CH2Cl2 extract was concentrated and purified by a silica gel column using 3% methanolic NH3 (7 M NH3 in methanol/97% CH2Cl2 as eluent to yield the desired product as a pale yellow oil (58%). 1H NMR (CDCl3) δ 8.530 (m, 1H, Ar), 7.604 (ddd, 1H, Ar), 7.330 (m, 2H, Ar), 7.128 (m, 2H, Ar), 7.027 (d, 2H, Ar), 6.969 (ddd, 1H, Ar), 3.892 (s, 2H, —CH2—), 3.837 (s, 2H, —CH2—), 2.523 (s, 1H, —CH—), 1.373 (s, 9H, —C(CH3)3). Mass Spec.=271.18 (M+H)+. the reaction mixture was refluxed under argon for 4 hr the solvent was removed the residue was redissolved in MeOH The solvent was then evaporated The solvent was evaporated followed by extraction with CH2Cl2 The CH2Cl2 extract was concentrated purified by a silica gel column

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

Procedure: To a stirred solution of 7 (3.8 g, 21 mmol) in 250 mL CH2Cl2, MnO2 (11 g, 126 mmol) was added. The reaction mixture was stirred overnight, filtered on Celite® and the solvent was distilled under reduced pressure. The crude product was purified by a silica gel column with 17% EtOAc/83% Hexane as eluents. The product was isolated as pale yellow oil (70% yield). 1H NMR (CDCl3) δ 7.286 (dd, 1H, Ar), 7.195 (ddd, 1H, Ar), 7.063 (d, 1H, Ar), 7.003 (ddd, 1H, Ar), 4.669 (s, 2H, —CH2—), 1.447 (s, 9H, —C(CH3)3). Mass Spec.=203.09 (M+H)++Na+. filtered on Celite® the solvent was distilled under reduced pressure The crude product was purified by a silica gel column with 17% EtOAc/83% Hexane as eluents