Cesium carbonate → Methyl 4-chloro-2-methylpyridine-3-carboxylate

Participants

Role	Name	HCID	Charge
Reactant	Cesium carbonate	HCID 10796	—
Reactant	Trimethylboroxine	HCID 574072	—
Reactant	Methyl 2,4-dichloropyridine-3-carboxylate	HCID 27282740	—
Catalyst	Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)	HCID 178418228	—
Solvent	Water	HCID 962	—
Solvent	1,4-Dioxane	HCID 31275	—
Product	Methyl 4-chloro-2-methylpyridine-3-carboxylate	HCID 84070460	31%

Reaction Conditions

Temperature	70 °C

Reaction Steps

A mixture of methyl 2,4-dichloronicotinate (2 g, 9.71 mmol), trimethylboroxine (1.462 g, 11.65 mmol), Cs2CO3 (6.33 g, 19.42 mmol) and PdCl2(dppf) (0.710 g, 0.971 mmol) in 1,4-dioxane (30 mL) and water (2 mL) was purged with nitrogen for 5 min and heated at 70° C. for 16 h. The reaction was concentrated under reduced pressure and purified by silica gel column chromatography (EtOAc-hexane mixture) to afford methyl 4-chloro-2-methylnicotinate (550 mg, 2.94 mmol, 31% yield) as a red oil. 1H NMR (300 MHz, CD3OD) δ ppm 8.44 (d, J=5.7 Hz, 1H), 7.43 (d, J=5.7 Hz, 1H), 3.98 (s, 3H), 2.54 (s, 3H).

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US08901305B2
Source dataset	uspto-grants-2014_12
ORD ID	ord-70b346e4c7f8438bb5ae98df09063c42
Source note	uspto-grants-2014_12