2-(Boc-amino)-5-bromopyridine → Tert-butyl 5-tert-butylpyridin-2-ylcarbamate

HRID 536725Notes

Reaction equation

C([Cu])#N.[C:4]([Mg]Cl)([CH3:7])([CH3:6])[CH3:5].Br[C:11]1[CH:12]=[CH:13][C:14]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[N:15][CH:16]=1>C1COCC1>[C:4]([C:11]1[CH:12]=[CH:13][C:14]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[N:15][CH:16]=1)([CH3:7])([CH3:6])[CH3:5]

Participants

Conditions

Temperature: -78 °C

Procedure

To a mixture of anhydrous CuCN (2.7 g, 30.4 mmol) in 100 mL of THF was added a solution of tert-butylmagnesium chloride (30.4 mL, 60.2 mmol, 2M solution in THF) under N2 at −78° C. After 20 minutes, tert-butyl 5-bromopyridin-2-ylcarbamate (2.1 g, 7.6 mmol, Aldrich) was added. The reaction mixture was stirred for 2 hours at −78° C. and then at room temperature for 12 hours. The mixture was quenched with saturated aqueous NH4OH and basified to pH 7 with 20% aqueous NaOH. The solid was filtered through a pad of Celite. The filtrate was extracted with ether and washed with water. The organic extract was dried over MgSO4 and concentrated. Purification by column chromatography (SiO2: 0-15% hexanes/ethyl acetate gradient) afforded 0.4 g of the title compound. MS (ESI+) m/z 251 (M+H)+.

Workup

waitat room temperature for 12 hours
customThe mixture was quenched with saturated aqueous NH4OH and basified to pH 7 with 20% aqueous NaOH
filtrationThe solid was filtered through a pad of Celite
extractionThe filtrate was extracted with ether
washwashed with water
extractionThe organic extract
dry with materialwas dried over MgSO4
concentrationconcentrated
customPurification by column chromatography (SiO2: 0-15% hexanes/ethyl acetate gradient)

Sources & evidence

ORD record: ord-aaf1b8fffb83416eaa953089430b7b12
Source dataset: uspto-grants-2014_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08859596B2

Reaction notes

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