Water → HCID 66600613, compound

HRID 1621896Notes

Reaction equation

[Cl-].[C:2]([O:6][C:7](=[O:10])[CH2:8][Zn+])([CH3:5])([CH3:4])[CH3:3].Br[C:12]1[CH:13]=[CH:14][C:15]([F:18])=[N:16][CH:17]=1.O>C1COCC1.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.Cl[Pd]Cl>[F:18][C:15]1[N:16]=[CH:17][C:12]([CH2:8][C:7]([O:6][C:2]([CH3:5])([CH3:4])[CH3:3])=[O:10])=[CH:13][CH:14]=1

Participants

Conditions

Temperature: 65 °C

Procedure

(2-tert-Butoxy-2-oxoethyl)zinc(II) chloride (0.5M in ethyl ether) (Rieke Metals, Inc., Lincoln, Nebr.; 73.9 mL, 36.9 mmol) was added to a mixture of 5-bromo-2-fluoropyridine (Acros, Morris Plains, N.J.; 2.92 mL, 28.4 mmol) and bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (Aldrich, St. Louis, Mo.; 0.201 g, 0.284 mmol) in THF (150 mL) and the resulting yellow solution was stirred at 65° C. for 1.5 h in a flask fitted with an air-cooled reflux condenser. Water (200 μL) was added to the reaction, and the resulting mixture was concentrated onto silica gel and chromatographically purified (silica gel, 0 to 30% EtOAc/hexanes) to provide tert-butyl 2-(6-fluoropyridin-3-yl)acetate (2.43 g, 11.50 mmol, 40.5% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.09 (s, 1H), 7.74 (td, J=8.0, 2.5 Hz, 1H), 6.90 (dd, J=8.4, 2.9 Hz, 1H), 3.52 (s, 2H), 1.44 (s, 9H). m/z (ESI, +ve) 212.1 (M+H)+.

Workup

customfitted with an air-cooled
temperaturereflux condenser
concentrationthe resulting mixture was concentrated onto silica gel
customchromatographically purified (silica gel, 0 to 30% EtOAc/hexanes)

Sources & evidence

ORD record: ord-431c8ff9b33f402ba0c9d5ae75adf452
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08772480B2

Reaction notes

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