Methylamine → 5-Iodo-N-methyl-4-pyrimidinamine

Participants

Role	Name	HCID	Charge
Reactant	Methylamine	HCID 6329	—
Reactant	Potassium Carbonate	HCID 11430	—
Reactant	Potassium Acetate	HCID 517044	—
Reactant	Bis(pinacolato)diborane	HCID 2733548	—
Reactant	4-Chloro-5-iodopyrimidine	HCID 11230204	—
Reactant	5-Iodo-N-methyl-4-pyrimidinamine	HCID 13261512	—
Catalyst	Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)	HCID 178418228	—
Solvent	Water	HCID 962	—
Solvent	Sodium Carbonate	HCID 10340	—
Solvent	1,4-Dioxane	HCID 31275	—
Product	5-Iodo-N-methyl-4-pyrimidinamine	HCID 13261512	—
Product	Ammonia methanol	HCID 21705897	—

Reaction Conditions

Temperature	105 °C

Reaction Steps

5-iodo-N-methylpyrimidin-4-amine (9A) was prepared from 4-chloro-5-iodopyrimidine and methylamine as described in WO2008100456. Compound 9A (37.5 mg, 0.160 mmol.) was then mixed with bis(pinacolato)diboron (46.6 mmg, 0.184 mmol), KOAc (78.3 mg, 0.798 mmol), and PdCl2(dppf) (32.6 mg, 0.040 mmol) in dioxane (2.0 mL). The mixture was heated at 105° C. overnight in a 5 mL sealed tube and then cooled to RT. The reaction was then treated with compound 5D (22.59 mg, 0.0800 mmol), K2CO3 (66.2 mg, 0.48 mmol), PdCl2(dppf) (16.3 mg, 0.020 mmol) and water (1.0 mL) and microwaved for 15 min at 125° C. The mixture was diluted with aq Na2CO3 and extracted with DCM. The organic extracts were dried over MgSO4 and concentrated. Chromatography (0-10% of (9:1 MeOH/NH3) in CH2Cl2) afforded (±)-9 (657 mg). LCMS m/z 312 (MH+).

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US08476274B2
Source dataset	uspto-grants-2013_07
ORD ID	ord-27e7e647c0c349ca980a7201249d3eda
Source note	uspto-grants-2013_07