Nitrogen → tert-Butyl 3-(3-methylpyridin-2-yl)benzoate

Participants

Role	Name	HCID	Charge
Reactant	Nitrogen	HCID 947	—
Reactant	Dichloromethane	HCID 6344	—
Reactant	Methanesulfonic Acid	HCID 6395	—
Reactant	Potassium Carbonate	HCID 11430	—
Reactant	Sodium Hydroxide	HCID 14798	—
Reactant	2-Bromo-3-methylpyridine	HCID 220832	—
Reactant	(3-((Tert-butoxy)carbonyl)phenyl)boronic acid	HCID 2773299	—
Catalyst	Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)	HCID 178418228	—
Solvent	Water	HCID 962	—
Solvent	Toluene	HCID 1140	—
Product	tert-Butyl 3-(3-methylpyridin-2-yl)benzoate	HCID 57516851	82%

Reaction Conditions

Temperature	80 °C

Reaction Steps

2-Bromo-3-methylpyridine (1.0 eq) was dissolved in toluene (12 vol). K2CO3 (4.8 eq) was added, followed by water (3.5 vol). The resulting mixture was heated to 65° C. under a stream of N2 for 1 hour. 3-(t-Butoxycarbonyl)phenylboronic acid (1.05 eq) and Pd(dppf)Cl2.CH2Cl2 (0.015 eq) were then added, and the mixture was heated to 80° C. After 2 hours, the heat was turned off, water was added (3.5 vol), and the layers were allowed to separate. The organic phase was then washed with water (3.5 vol) and extracted with 10% aqueous methanesulfonic acid (2 eq MsOH, 7.7 vol). The aqueous phase was made basic with 50% aqueous NaOH (2 eq) and extracted with EtOAc (8 vol). The organic layer was concentrated to afford crude tert-butyl-3-(3-methylpyridin-2-yl)benzoate (82%) that was used directly in the next step.

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US09314455B2
Source dataset	uspto-grants-2016_04
ORD ID	ord-2a0e04082bd94c589b438bc473f513c3
Source note	uspto-grants-2016_04