3,4-Pyridinediamine,N3-(phenylmethyl)-

General procedure: Step 1: A vial equipped with a magnetic stir bar was charged with the orthohaloaminopyridineand BrettPhos G1 precatalyst (6 mol percent). The vial was sealedwith a teflon screw cap, and evacuated and backfilled with argon three times. Theamine (1 to 1.5 mol eq) was added via syringe, followed by LiHMDS solution (1M in THF, 2.5 mol eq). Amines that were solid at room temperature were addedwith the catalyst. The reaction mixture was stirred at 40 °C for 4-18 h, until LC/MSindicated complete conversion of the starting material. The mixture was cooled toroom temperature, diluted with dichloromethane, and poured into water. Theorganic phase was separated and the aqueous phase was extracted twice more withdichloromethane. The combined organic phases were dried over Na2SO4. Thesolvent was removed under reduced pressure.General procedure: The vial containing the crude diaminopyridine was equipped with a magnetic stir bar and sealed with a teflon screw cap. Aldehyde (2 mol eqwith respect to the theoretical yield of the first reaction) and then nBuOH was added via syringe to give a diaminopyridine concentration of 0.3 M based on the theoretical yield of the first reaction. The reaction mixture was stirred at 110 C for 18-24 h with needle inserted in septum to expose reaction to air. The mixture was cooled to room temperature, diluted with ethyl acetate, and poured into aqueous saturated NaHCO3. The organic phase was separated and the aqueous phase was extracted twice more into ethyl acetate. The combined organic phases were driedover Na2SO4. The solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel, typically using EtOAc, 0 ->10% MeOH.General procedure: The vial containing the crude diaminopyridine was equipped with a magnetic stir bar and sealed with a teflon screw cap. Aldehyde (2 mol eqwith respect to the theoretical yield of the first reaction) and then nBuOH was added via syringe to give a diaminopyridine concentration of 0.3 M based on the theoretical yield of the first reaction. The reaction mixture was stirred at 110 C for 18-24 h with needle inserted in septum to expose reaction to air. The mixture was cooled to room temperature, diluted with ethyl acetate, and poured into aqueous saturated NaHCO3. The organic phase was separated and the aqueous phase was extracted twice more into ethyl acetate. The combined organic phases were driedover Na2SO4. The solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel, typically using EtOAc, 0 ->10% MeOH.General procedure: The vial containing the crude diaminopyridine was equipped with a magnetic stir bar and sealed with a teflon screw cap. Aldehyde (2 mol eqwith respect to the theoretical yield of the first reaction) and then nBuOH was added via syringe to give a diaminopyridine concentration of 0.3 M based on the theoretical yield of the first reaction. The reaction mixture was stirred at 110 C for 18-24 h with needle inserted in septum to expose reaction to air. The mixture was cooled to room temperature, diluted with ethyl acetate, and poured into aqueous saturated NaHCO3. The organic phase was separated and the aqueous phase was extracted twice more into ethyl acetate. The combined organic phases were driedover Na2SO4. The solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel, typically using EtOAc, 0 ->10% MeOH.General procedure: The vial containing the crude diaminopyridine was equipped with a magnetic stir bar and sealed with a teflon screw cap. nBuOH was added via syringe to give a diaminopyridine concentration of 0.3 M based on the theoretical yield of the first reaction. Triethyl orthoformate/orthoacetate (5 mol eq with respect to the theoretical yield of the first reaction) was added via syringe. Formic/acetic acid (1 mol eq with respect to the theoretical yield of the first reaction) was added via micropipette. The reaction mixture was stirred at 110 Cfor 18-24 h. The mixture was cooled to room temperature, diluted with ethylacetate, and poured into aqueous saturated NaHCO3. The organic phase was separated and the aqueous phase was extracted twice more into ethyl acetate. The combined organic phases were dried over Na2SO4. The solvent was removed under reduced pressure. The residue was purified by flash column chromatography onsilica gel, typically using EtOAc, 0 -> 10% MeOH.General procedure: Step 1: A vial equipped with a magnetic stir bar was charged with the orthohaloaminopyridineand BrettPhos G1 precatalyst (6 mol %). The vial was sealedwith a teflon screw cap, and evacuated and backfilled with argon three times. Theamine (1 to 1.5 mol eq) was added via syringe, followed by LiHMDS solution (1M in THF, 2.5 mol eq). Amines that were solid at room temperature were addedwith the catalyst. The reaction mixture was stirred at 40 C for 4-18 h, until LC/MSindicated complete conversion of the starting material. The mixture was cooled toroom temperature, diluted with dichloromethane, and poured into water. Theorganic phase was separated and the aqueous phase was extracted twice more withdichloromethane. The combined organic phases were dried over Na2SO4. Thesolvent was removed under reduced pressure.

Molecular Weight:199.25
XLogP3:1.6
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:199.110947427
Monoisotopic Mass:199.110947427
Topological Polar Surface Area:50.9
Heavy Atom Count:15
Complexity:178
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes