Diethyl Ether → Tert-butyl 2-(6-fluoro-5-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-YL)pyridin-3-YL)acetate

HRID 1812388Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([B:9]2[O:16][C:15](=[O:17])[CH2:14][N:13]([CH3:18])[CH2:12][C:11](=[O:19])[O:10]2)[C:5]([F:8])=[N:6][CH:7]=1.[Cl-].[C:21]([O:25][C:26](=[O:29])[CH2:27][Zn+])([CH3:24])([CH3:23])[CH3:22].CCOCC>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.O1CCOCC1>[F:8][C:5]1[N:6]=[CH:7][C:2]([CH2:27][C:26]([O:25][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:29])=[CH:3][C:4]=1[B:9]1[O:16][C:15](=[O:17])[CH2:14][N:13]([CH3:18])[CH2:12][C:11](=[O:19])[O:10]1

Participants

Conditions

Temperature: 80 °C

Procedure

To 2-(5-bromo-2-fluoropyridin-3-yl)-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione (2.79 g, 8.43 mmol) was added dioxane (84 mL), bis-(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (0.299 g, 0.422 mmol) and (2-tert-butoxy-2-oxoethyl)zinc(II) chloride in ether (25.3 mL, 12.65 mmol) (Rieke Metals), and the resulting mixture was sparged with nitrogen for 5 min at ambient temperature. The reaction mixture was then heated to 80° C. for 2 h. The reaction mixture was subsequently cooled to ambient temperature, adsorbed onto silica gel, and purified via flash chromatography (silica gel) with 100% DCM to 5% MeOH/DCM to give the title compound (62% yield) as a beige solid. m/z (ESI, +ve ion) 367.2 (M+H)+.

Workup

customthe resulting mixture was sparged with nitrogen for 5 min at ambient temperature
temperatureThe reaction mixture was subsequently cooled to ambient temperature
custompurified via flash chromatography (silica gel) with 100% DCM to 5% MeOH/DCM

Sources & evidence

ORD record: ord-2b1b8fe22bb44054b888e7e9a624b866
Source dataset: uspto-grants-2013_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08362241B2

Reaction notes

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