Cesium carbonate → Dimethyl 5-(4-pyridyl)-1-methyl-6-oxo-1,6-dihydropyridine-3,4-dicarboxylate

HRID 1752596Notes

Reaction equation

HRID 1752596 reaction equation
[CH3:1][N:2]1[CH:7]=[C:6]([C:8]([OH:10])=[O:9])[C:5]([C:11]([O:13][CH3:14])=[O:12])=[C:4](Cl)[C:3]1=[O:16].[N:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1.[C:26]([O-])([O-])=O.[Cs+].[Cs+]>COCCOC.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[N:17]1[CH:22]=[CH:21][C:20]([C:4]2[C:3](=[O:16])[N:2]([CH3:1])[CH:7]=[C:6]([C:8]([O:10][CH3:26])=[O:9])[C:5]=2[C:11]([O:13][CH3:14])=[O:12])=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 904220091-Methyl-2-oxo-1,2-dihydro-3-chloro-4-methoxycarbonyl-pyridine-5-carboxylic acid

Product 1

HCID 125500102Dimethyl 5-(4-pyridyl)-1-methyl-6-oxo-1,6-dihydropyridine-3,4-dicarboxylateYield 40%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

To a mixture of compound (4) (3.5 g, 13.5 mmol), pyridine-4-yl-boronic acid (4.9 g, 40.4 mmol), Pd(dppf)Cl2 (1.1 g, 1.3 mmol) and Cs2CO3 (13.1 g, 40.4 mmol) in DME/water (4/1, 80 ml) was stirred at 90° C. overnight. The solution was concentrated and purified by column chromatography on silica gel (DCM/MeOH=100:1) to give title compound as off-white solid (1.6 g, 40%). LC-MS (ESI+): m/e 303 (M+H)+, Rt: 0.561 min.

Workup

  1. concentrationThe solution was concentrated
  2. custompurified by column chromatography on silica gel (DCM/MeOH=100:1)

Sources & evidence

ORD record
ord-ea74dd792497452e9b3a8837eb31d92d
Source dataset
uspto-grants-2015_10
Patent number
US09163019B2

Reaction notes

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