Reaction SMILES: [Br:1][C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-])=O)=[C:6]([CH:9]=1)[CH:7]=O.C(Cl)Cl.C[O:17][CH:18](OC)[CH2:19][CH:20](OC)OC.C1(C)C=CC=CC=1>CO.Cl.[Fe].CC(O)=O>[Br:1][C:2]1[CH:9]=[C:6]2[C:5](=[CH:4][CH:3]=1)[N:10]=[CH:20][C:19]([CH:18]=[O:17])=[CH:7]2
Reactant: COC(CC(OC)OC)OC
Reactant: O=Cc1cc(Br)ccc1[N+](=O)[O-]
Agent: [Fe]
Agent: Cl
Solvent: CO
Solvent: ClCCl
Solvent: Cc1ccccc1
Product: O=Cc1cnc2ccc(Br)cc2c1
Temperature: 70 °C
Reaction time: 1 h

Procedure:
5-Bromo-2-nitrobenzaldehyde (6.03 g, 26.2 mmol) was dissolved in MeOH (200 mL) and treated with 5N HCl (10 mL). The mixture was heated to 70° C. and iron powder (7.32 g, 131 mmol) was added in five portions every 5 min. The reaction was monitored by TLC, and upon completion, the reaction was cooled, DCM (200 mL) added and filtered through a pad of celite. The filtrate was concentrated under reduced pressure to about 150 mL. To this material, a solution of 1,1,3,3-tetramethoxypropane (9.52 ml, 57.7 mmol) in 5N HCl (10 mL) pre-mixed for 45 min was added. The reaction mixture was stirred at 80° C. for 60 min. Toluene (100 mL) and HOAc (40 mL) were added and the solution was heated to 110° C. for 3 h, then cooled and evaporated to dryness under reduced pressure. The crude material was purified using silica chromatography (20-60% ethyl acetate in hexane gradient) to provide 6-bromoquinoline-3-carbaldehyde. Step 2 6-Bromoquinoline-3-carbaldehyde (2.8 g, 12.0 mmol) and methyl(triphenylphosphoranylidene)acetate (4.0 g, 12.0 mmol) were dissolved in dry THF (50 mL) and heated to 50° C. After 40 min the solution was evaporated to dryness under reduced pressure. Purification using silica chromatography (hexane to 60% EtOAc in hexane gradient) gave methyl 3-(6-bromoquinolin-3-yl)acrylate as a mixture of E and Z isomers. Step 3 Methyl 3-(6-bromoquinolin-3-yl)acrylate (0.91 g, 3.1 mmol) 2-methylphenyl boronic acid (0.61 g), potassium acetate (1.0 g) and bis(4-(di-tert-butylphosphino)-N,N-dimethylbenzenamine)dichloropalladium (II) (0.19 g) were suspended in ethanol (70 mL) and water (5 mL) and heated to reflux for 90 min. LC/MS showed the bromoquinoline had been consumed the reaction was evaporated to dryness under reduced pressure. The crude was partitioned between EtOAc and water. The organic layer was dried with magnesium sulfate, evaporated to dryness under reduced pressure and purified using silica chromatography (hexane to EtOAc gradient) to give methyl 3-(6-o-tolylquinolin-3-yl)acrylate. Step 4 LiOH monohydrate (0.42 g) (solution in water, 10 mL) was added to a solution of methyl 3-(6-o-tolylquinolin-3-yl)acrylate (0.32 g, 1.05 mmol) in MeOH (50 mL) and heated to 50° C. The reaction was monitored by TLC and once the ester had been consumed, 5N HCl (2 mL) was added and the mixture was concentrated to dryness under reduced pressure. The crude acid was dried under high vacuum then dissolved in thionyl chloride (30 mL) and heated to 80° C. for 1 h. The solution was evaporated to dryness under reduced pressure and the crude acid chloride dissolved in DCM (50 mL). A solution of N-methylcyclohexylamine (660 uL) and DIEA (850 uL) in DCM (10 mL) was added slowly and the mixture stirred for 15 min. Additional DCM (50 mL) and water (80 mL) were added and the phases were separated. The organic layer was dried with magnesium sulfate and evaporated to dryness under reduced pressure. Purification using silica chromatography (hexane to EtOAc gradient) gave the desired amide. This material was dissolved in MeOH (50 mL) and treated with 10 wt % palladium on carbon (0.12 g). The mixture was hydrogenated at 50 psi for 30 min until the reduction was complete by LC/MS. The mixture was filtered through a pad of celite and evaporated to dryness under reduced pressure. Purification using silica chromatography (hexane to EtOAc gradient) provided N-cyclohexyl-N-methyl-3-(6-o-tolylquinolin-3-yl)propanamide. Step 5 N-Cyclohexyl-N-methyl-3-(6-o-tolylquinolin-3-yl)propanamide (0.13 g) and m-chloroperbenzoic acid (0.11 g) were dissolved in chloroform and heated to reflux for 10 min. DCM (30 mL) and 1N NaOH (70 mL) were added and the phases mixed and separated. The organic layer was dried with magnesium sulfate and evaporated to dryness under reduced pressure. The crude N-oxide was dissolved in a mixture of trifluoromethylbenzene (20 mL) and tert-butylamine (0.20 mL), then p-toluenesulfonic anhydride (0.15 g) was added. The mixture was stirred until LC/MS analysis showed the desired amine had formed. Water (100 mL), 5N NaOH (30 mL), and DCM (70 mL) were added and the phases were separated. The organic layer was dried with magnesium sulfate before evaporating to dryness. Purification using silica chromatography (hexane to EtOAc gradient) gave the 2-(tert-butylamino)-quinoline. This material was dissolved in TFA (30 mL) and heated to reflux. After the deprotection was complete by LC/MS, the solution was evaporated to dryness under reduced pressure and the crude material was basified using saturated sodium bicarbonate and DCM. Silica purification (0-10% MeOH in DCM gradient) gave 3-(2-amino-6-o-tolylquinolin-3-yl)-N-cyclohexyl-N-methylpropanamide. MS (ESI, pos. ion) m/z: 402 (M+1).