Ethyl Acetate → Tert-butyl 4-(4-aminophenyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 1992030Notes

Reaction equation

[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11](OS(C(F)(F)F)(=O)=O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC1(C)C(C)(C)OB([C:30]2[CH:35]=[CH:34][C:33]([NH2:36])=[CH:32][CH:31]=2)O1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>C1(C)C=CC=CC=1.C(O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11]([C:30]2[CH:35]=[CH:34][C:33]([NH2:36])=[CH:32][CH:31]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 80 °C

Procedure

To a mixture of 4-trifluoromethanesulfonyloxy-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (Synthesis, 993, (1991), 7.4 g, 22 mmol), 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylamine (4.0 g, 18 mmol) and Pd(PPh3)4 (2.3 g, 2.0 mmol) in 160 mL of toluene and 80 mL of absolute ethanol under Ar was added 2.0 M aq Na2CO3 solution (80 mL, 160 mmol). The resulting mixture was stirred at 80° C. for 3 h and then cooled to RT. After adding 600 mL of EtOAc, the mixture was washed with 1 M NaOH (250 mL), H2O (2×250 mL), brine (300 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (20% EtOAc/hexane) gave 3.20 g (63%) of the title compound as a hard yellow foam: Mass spectrum (ESI, m/z): Calcd. for C16H22N2O2, 275.2 (M+H), found 275.1.

Workup

temperaturecooled to RT
washthe mixture was washed with 1 M NaOH (250 mL), H2O (2×250 mL), brine (300 mL)
dry with materialdried (Na2SO4)
customRemoval of the solvent under reduced pressure

Sources & evidence

ORD record: ord-df28d9eacec3437fa6f31007e09a72b2
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07645755B2

Reaction notes

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