bis(2-methylphenyl)methanamine

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

Procedure: In air, 2-pyridinecarboxaldehyde (36.0 mg, 32.0 μL, 0.336 mmol, 1.00 equiv) was added to a solution of di-o-tolylmethanamine (73.1 mg, 0.346 mmol, 1.03 equiv) in CH2Cl2 (5 mL). After heating at reflux for 30 min with azeotropic removal of water using a Dean-Stark trap, the reaction mixture was concentrated under reduced pressure and dried under high vacuum to give ligand (L-3), (E)-N-(Pyridin-2-ylmethylene)-1,1-dio-tolylmethanamine, as a yellow oil (0.102 g, 98% yield). After heating the reaction mixture was concentrated under reduced pressure dried under high vacuum

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The following procedure was adapted from Zhang et al. (Org. Lett. 2008, 10, 5429-5432). To Mg turnings (1.53 g, 63.0 mmol, 1.50 equiv) in THF (50 mL) in an oven-dried round-bottom flask fitted with a reflux condenser was added 2-methyliodobenzene (11.0 g, 6.40 mL, 1.20 equiv) dropwise. The reaction mixture was heated to reflux for 1 h. To the reaction mixture was added o-tolunitrile (4.94 g, 5.00 mL, 42.2 mmol, 1.00 equiv) and the reaction mixture was heated to reflux for 22 h. The reaction mixture was cooled to 23° C. and a suspension of LiAlH4 (1.97 g, 51.9 mmol, 1.23 equiv) in THF (50 mL) was added and the reaction mixture was heated to reflux for 25 h. The reaction mixture was cooled to 23° C. and H2O (2 mL) was added dropwise. A solution of NaOH (2 mL, 1 M in H2O) was added slowly and 8 mL H2O was added. The reaction mixture was filtered through a celite pad, eluting with EtOAc, and concentrated. The residue was purified by Kugelrohr distillation (240 mTorr, 200° C.) to give di-o-tolylmethanamine as a yellow oil (8.52 g, 96% yield). The reaction mixture was heated to reflux for 1 h the reaction mixture was heated to reflux for 22 h was added the reaction mixture was heated to reflux for 25 h The reaction mixture was cooled to 23° C. The reaction mixture was filtered through a celite pad eluting with EtOAc concentrated The residue was purified by Kugelrohr distillation (240 mTorr, 200° C.)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound of Example 554F (100 mg, 0.47 mmol) was dissolved in 2 mL of 1,2-dichloroethane. To this solution at −78° C. was added Et3N (0.05 mL) and then dropwise bromoacetyl bromide (40 mL, 0.47 mmol in 1 mL of 1,2-dichloroethane). The reaction mixture was stirred at −78° C. for 10 min, then at r.t. for 2 h., diluted with water (10 mL), and extracted with 1,2-dichloroethane (2×25 mL). The combined organic layers were concentrated to give the bromoacetamide as a white solid (184 mg, 96%) suitable for further use without additional purification. at r.t. for 2 h. extracted with 1,2-dichloroethane (2×25 mL) The combined organic layers were concentrated

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

Procedure: In air, 2-pyridinecarboxaldehyde (36.0 mg, 32.0 μL, 0.336 mmol, 1.00 equiv) was added to a solution of di-o-tolylmethanamine (73.1 mg, 0.346 mmol, 1.03 equiv) in CH2Cl2 (5 mL). After heating at reflux for 30 min with azeotropic removal of water using a Dean-Stark trap, the reaction mixture was concentrated under reduced pressure and dried under high vacuum to give ligand (L-3), (E)-N-(Pyridin-2-ylmethylene)-1,1-dio-tolylmethanamine, as a yellow oil (0.102 g, 98% yield). After heating the reaction mixture was concentrated under reduced pressure dried under high vacuum

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The following procedure was adapted from Zhang et al. (Org. Lett. 2008, 10, 5429-5432). To Mg turnings (1.53 g, 63.0 mmol, 1.50 equiv) in THF (50 mL) in an oven-dried round-bottom flask fitted with a reflux condenser was added 2-methyliodobenzene (11.0 g, 6.40 mL, 1.20 equiv) dropwise. The reaction mixture was heated to reflux for 1 h. To the reaction mixture was added o-tolunitrile (4.94 g, 5.00 mL, 42.2 mmol, 1.00 equiv) and the reaction mixture was heated to reflux for 22 h. The reaction mixture was cooled to 23° C. and a suspension of LiAlH4 (1.97 g, 51.9 mmol, 1.23 equiv) in THF (50 mL) was added and the reaction mixture was heated to reflux for 25 h. The reaction mixture was cooled to 23° C. and H2O (2 mL) was added dropwise. A solution of NaOH (2 mL, 1 M in H2O) was added slowly and 8 mL H2O was added. The reaction mixture was filtered through a celite pad, eluting with EtOAc, and concentrated. The residue was purified by Kugelrohr distillation (240 mTorr, 200° C.) to give di-o-tolylmethanamine as a yellow oil (8.52 g, 96% yield). The reaction mixture was heated to reflux for 1 h the reaction mixture was heated to reflux for 22 h was added the reaction mixture was heated to reflux for 25 h The reaction mixture was cooled to 23° C. The reaction mixture was filtered through a celite pad eluting with EtOAc concentrated The residue was purified by Kugelrohr distillation (240 mTorr, 200° C.)