Pyruvic Acid → 5-(methoxycarbonyl)-1H-pyrrolo(3,2-b)pyridine-2-carboxylic acid

HRID 526012Notes

Reaction equation

[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([O:10][CH3:11])=[O:9])=[N:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:31]([OH:36])(=[O:35])[C:32]([CH3:34])=O.C(N(CC)CC)C>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:11][O:10][C:8]([C:5]1[N:6]=[C:7]2[CH:34]=[C:32]([C:31]([OH:36])=[O:35])[NH:1][C:2]2=[CH:3][CH:4]=1)=[O:9]

Participants

Conditions

Temperature: 100 °C

Procedure

Methyl 5-aminopyridine-2-carboxylate (1.2 g, 5.2 mmol) and triphenylphosphine (1.5 g, 5.7 mmol) were initially charged in 10 ml of DMF, and pyruvic acid (1.83 g, 20.8 mmol), palladium(II) acetate (279 mg, 1.2 mmol) and triethylamine (2.6 g, 26 mmol) were added. The reaction mixture was stirred at a temperature of 100° C. for four hours, then cooled, concentrated on a rotary evaporator and taken up in ethyl acetate, water was added and the mixture was shaken. The aqueous phase was concentrated on a rotary evaporator and then triturated with a little cyclohexane. This gave 0.5 g (38% of theory) of 5-(methoxycarbonyl)-1H-pyrrolo[3,2-b]pyridine-2-carboxylic acid. HPLC-MS: log P=0.44; mass (m/z): 221.0 (M+H)+; 1HNMR (D6-DMSO): δ 3.89 (s, 3H), 7.20 (s, 1H), 7.90-7.98 (m, 2H), 10 (broad, 1H), 12.24 (s, 1H).

Workup

temperaturecooled
concentrationconcentrated on a rotary evaporator
additionwater was added
stirringthe mixture was shaken
concentrationThe aqueous phase was concentrated on a rotary evaporator
customtriturated with a little cyclohexane

Sources & evidence

ORD record: ord-bc6851da7346401ba853887ee8b2972f
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09345247B2

Reaction notes

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