tert-Butylsulfinamide, (R)-(+)- → HCID 90301392、化合物

HRID 930299ノート

反応式

HRID 930299 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([C:9](=O)[CH3:10])[C:5]([F:8])=[N:6][CH:7]=1.[CH3:12][C:13]([S@:16]([NH2:18])=[O:17])([CH3:15])[CH3:14]>C1COCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4](/[C:9](=[N:18]\[S@@:16]([C:13]([CH3:15])([CH3:14])[CH3:12])=[O:17])/[CH3:10])[C:5]([F:8])=[N:6][CH:7]=1

参加物

6

反応物 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 401519061-(5-Bromo-2-fluoropyridin-3-yl)ethan-1-one

生成物 1

HCID 90301392HCID 90301392、化合物収率 99%

試薬・触媒・溶媒 3

HCID 76524Titanium tetraethoxide触媒HCID 8028Tetrahydrofuran溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

A mixture of 1-(5-bromo-2-fluoropyridin-3-yl)ethanone (5a, synthesized according to procedures described in WO2009016460; 11 g, 50.5 mmol), (R)-2-methylpropane-2-sulfinamide (Ak Scientific, 12.23 g, 101 mmol) and titanium (IV) ethoxide (Aldrich, 26.1 ml, 126 mmol) in THF (100 mL) was heated to reflux for 2 h. The mixture was cooled to room temperature, and brine (200 mL) was added. The suspension was vigorously stirred for 10 min. The suspension was filtered through a pad of silica gel and the organic phase was separated. The aqueous phase was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by silica gel chromatography (gradient 0-20% EtOAc/hexanes) to afford the title compound as a bright yellow oil (16 g, 49.8 mmol, 99% yield). MS m/z=320.8 [M+H]+; Calculated for C11H14BrFN2OS: 320.0

後処理

  1. temperaturewas heated
  2. temperatureto reflux for 2 h
  3. filtrationThe suspension was filtered through a pad of silica gel
  4. customthe organic phase was separated
  5. extractionThe aqueous phase was extracted with EtOAc
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel chromatography (gradient 0-20% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-775ea774c36c48e28eb64fde89937eba
出典データセット
uspto-grants-2016_03
特許番号
US09296734B2

反応ノート

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