Allyl bromide → (S)-N-((R)-1-(2-bromo-5-fluorophenyl)but-3-en-1-yl)-2-methylpropane-2-sulfinamide

HRID 513037

Reaktionsgleichung

Reaktionsgleichung von HRID 513037
[Br:1][C:2]1[CH:15]=[CH:14][C:13]([F:16])=[CH:12][C:3]=1/[CH:4]=[N:5]/[S@:6]([C:8]([CH3:11])([CH3:10])[CH3:9])=[O:7].[In].[CH2:18](Br)[CH:19]=[CH2:20].C([O-])(O)=O.[Na+]>[Na+].[Br-]>[Br:1][C:2]1[CH:15]=[CH:14][C:13]([F:16])=[CH:12][C:3]=1[C@H:4]([NH:5][S@:6]([C:8]([CH3:11])([CH3:10])[CH3:9])=[O:7])[CH2:20][CH:19]=[CH2:18]

Komponenten

6

Edukt 4

HCID 7841Allyl bromideHCID 516892Sodium BicarbonateHCID 5359967IndiumHCID 71725992(NE,S)-N-[(2-bromo-5-fluorophenyl)methylidene]-2-methylpropane-2-sulfinamide

Produkt 1

HCID 66684297(S)-N-((R)-1-(2-bromo-5-fluorophenyl)but-3-en-1-yl)-2-methylpropane-2-sulfinamide

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 253881Sodium BromideLösungsmittel

Versuchsvorschrift

To a stirred suspension of (S,E)-N-(2-bromo-5-fluorobenzylidene)-2-methylpropane-2-sulfinamide (I-44) (153 mg, 0.50 mmol) and indium powder (230 mg, 2.0 mmol) in saturated NaBr (10 mL, aq) was added allyl bromide (169 μL, 2.0 mmol). After stirring 36 hours the reaction mixture was charged with saturated aqueous NaHCO3 and stirred 30 minutes. The mixture was extracted with EtOAc and combined extracts were washed with brine, dried over sodium sulfate and concentrated. The residue was purified by silica gel chromatography with EtOAc/Hex (5-35%) as eluent to yield the (S)-N-((R)-1-(2-bromo-5-fluorophenyl)but-3-en-1-yl)-2-methylpropane-2-sulfinamide (I-45A) as a clear oil. 1H NMR (400 MHz, CDCl3) δ 7.52 (dd, J=5.3, 8.8 Hz, 1 H), 7.14 (dd, J=3.1, 9.8 Hz, 1 H), 6.88 (ddd, J=3.1, 7.7, 8.7 Hz, 1 H), 5.77 (dddd, J=6.1, 8.2, 10.9, 16.6 Hz, 1 H), 5.28-5.16 (m, 2 H), 4.98-4.89 (m, 1 H), 3.74 (s, 1 H), 2.76-2.63 (m, 1 H), 2.39 (dt, J=8.3, 14.2 Hz, 1 H), 1.24 (s, 9 H). 19F NMR (376 MHz, CDCl3) δ −113.87. MS m/z 348.0, 350.0 (M+1)+.

Aufarbeitung

  1. stirringstirred 30 minutes
  2. extractionThe mixture was extracted with EtOAc
  3. washwere washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel chromatography with EtOAc/Hex (5-35%) as eluent

Quellen und Nachweise

ORD-Eintrag
ord-b994ba6b2cf64caabfafeb01536ab101
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09102671B2

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