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

HRID 513037

반응식

HRID 513037 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 253881Sodium Bromide용매

실험 절차

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)+.

후처리

  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

출처 및 근거

ORD 기록
ord-b994ba6b2cf64caabfafeb01536ab101
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09102671B2

연결된 노트

불러오는 중…