tert-Butylsulfinamide, (R)-(+)- → (NE,R)-N-[[4-(1,1-difluoroethyl)-2-fluorophenyl]methylidene]-2-methylpropane-2-sulfinamide

HRID 57461

Reaction equation

[F:1][C:2]([C:5]1[CH:12]=[CH:11][C:8]([CH:9]=O)=[C:7]([F:13])[CH:6]=1)([F:4])[CH3:3].[CH3:14][C:15]([S@:18]([NH2:20])=[O:19])([CH3:17])[CH3:16]>ClCCCl.S([O-])([O-])(=O)=O.[Cu+2]>[F:1][C:2]([C:5]1[CH:12]=[CH:11][C:8](/[CH:9]=[N:20]/[S@@:18]([C:15]([CH3:17])([CH3:16])[CH3:14])=[O:19])=[C:7]([F:13])[CH:6]=1)([F:4])[CH3:3]

Participants

Conditions

Temperature: 55 °C

Procedure

To a mixture of 4-(1,1-difluoroethyl)-2-fluorobenzaldehyde (693 mg, from Step 4) and (R)-2-methylpropane-2-sulfinamide (513 mg, 4.24 mmol) in DCE (12.9 mL) was added copper(II) sulfate (882 mg, 5.52 mmol). The reaction mixture was placed in a pre-heated oil bath (55° C.) and heated for ˜2 d. The mixture was allowed to cool to room temperature, filtered through a pad of celite and rinsed with DCE. The combined filtrates were concentrated under reduced pressure. The residue was purified by column chromatography [SiO2, 24 g, heptane/ethyl acetate] providing (R,E)-N-(4-(1,1-difluoroethyl)-2-fluorobenzylidene)-2-methylpropane-2-sulfinamide (497 mg) as a yellow oil. LCMS m/z 292.1 (M+H)+, Rt 0.97 min.

Workup

customThe reaction mixture was placed in a pre-heated oil bath
temperatureto cool to room temperature
filtrationfiltered through a pad of celite
washrinsed with DCE
concentrationThe combined filtrates were concentrated under reduced pressure
customThe residue was purified by column chromatography [SiO2, 24 g, heptane/ethyl acetate]

Sources & evidence

ORD record: ord-574f6ecd80b143f8b47b401ea8b0dd74
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09434719B2

Linked notes

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