Dimethylformamide → 3-Tert-butyldimethylsilyloxy-2,5-difluorobenzaldehyde

HRID 1662561Notes

Reaction equation

[C:1]([Si:5]([O:8][C:9]1[CH:14]=[C:13]([F:15])[CH:12]=[CH:11][C:10]=1[F:16])([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C([Li])(CC)C.CN([CH:25]=[O:26])C>C1COCC1>[Si:5]([O:8][C:9]1[C:10]([F:16])=[C:11]([CH:12]=[C:13]([F:15])[CH:14]=1)[CH:25]=[O:26])([C:1]([CH3:4])([CH3:2])[CH3:3])([CH3:7])[CH3:6]

Participants

Conditions

Temperature: -78 °C

Procedure

A 500 mL round bottom flask was charged with 90.A (8.60 g, 35.2 mmol) and THF (70 mL) and cooled to −78° C. under N2. To the cold solution was added sec-butyllithium (1.4 M in cyclohexane) (available from Aldrich) (27.7 mL, 38.7 mmol) dropwise. The mixture was stirred for 30 minutes, and to it was added DMF (4.09 mL, 52.8 mmol) dropwise. The mixture was stirred for 30 minutes at −78° C., warmed to room temperature over 30 minutes, quenched with 1 N HCl, and diluted with EtOAc. The organic layers were washed with water and brine, dried (MgSO4), and concentrated. The crude product was purified by silica gel flash chromatography (0-5% EtOAc/hexane) to afford 90.B (5.71 g, 59.6% yield) as a colorless oil.

Workup

stirringThe mixture was stirred for 30 minutes at −78° C.
temperaturewarmed to room temperature over 30 minutes
customquenched with 1 N HCl
additiondiluted with EtOAc
washThe organic layers were washed with water and brine
dry with materialdried (MgSO4)
concentrationconcentrated
customThe crude product was purified by silica gel flash chromatography (0-5% EtOAc/hexane)

Sources & evidence

ORD record: ord-8df2597ef5f3445b8caabf0b050ad5af
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08030354B2

Reaction notes

Loading…