Triacetoxyperiodinane → (R)-N-((S)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-oxobutan-2-yl)-2-methylpropane-2-sulfinamide

HRID 930357ノート

反応式

HRID 930357 の反応式
[Br:1][C:2]1[N:7]=[C:6]([C@:8]([NH:15][S@@:16]([C:18]([CH3:21])([CH3:20])[CH3:19])=[O:17])([CH2:12][CH2:13][OH:14])[CH:9]([F:11])[F:10])[C:5]([F:22])=[CH:4][CH:3]=1.BrC1N=C([C@@](N[S@@](C(C)(C)C)=O)(CCO)C(F)F)C(F)=CC=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.BrC1N=C([C@](N[S@@](C(C)(C)C)=O)(CC=O)C(F)F)C(F)=CC=1>C(Cl)Cl.O>[Br:1][C:2]1[N:7]=[C:6]([C@@:8]([NH:15][S@@:16]([C:18]([CH3:20])([CH3:19])[CH3:21])=[O:17])([CH2:12][CH:13]=[O:14])[CH:9]([F:11])[F:10])[C:5]([F:22])=[CH:4][CH:3]=1

参加物

7

反応物 4

HCID 159087TriacetoxyperiodinaneHCID 86732175(R)-N-((S)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-hydroxybutan-2-yl)-2-methylpropane-2-sulfinamideHCID 86732176(R)-N-((R)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-hydroxybutan-2-yl)-2-methylpropane-2-sulfinamideHCID 86732178(R)-N-((R)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-oxobutan-2-yl)-2-methylpropane-2-sulfinamide

生成物 1

HCID 86732177(R)-N-((S)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-oxobutan-2-yl)-2-methylpropane-2-sulfinamide収率 70.9%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

To a solution of the mixture of (R)-N-((R)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-hydroxybutan-2-yl)-2-methylpropane-2-sulfinamide and (R)-N-((S)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-hydroxybutan-2-yl)-2-methylpropane-2-sulfinamide (0.17 g, 0.422 mmol) in DCM (2.1 ml) was added Dess-Martin periodinane (0.215 g, 0.506 mmol). The reaction mixture was stirred at RT. After 1 h, the mixture was diluted with water and extracted with DCM three times. The organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude was purified by silica gel chromatography: 40 g Grace column, 0-50% EtOAc-hexane in 20 min to give a 3:1 mixture of (R)-N-((R)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-oxobutan-2-yl)-2-methylpropane-2-sulfinamide and (R)-N-((S)-2-(6-bromo-3-fluoropyridin-2-yl)-1,1-difluoro-4-oxobutan-2-yl)-2-methylpropane-2-sulfinamide (0.12 g, 0.299 mmol, 70.9% yield) was obtained as a colorless oil. MS m/z=401, 403 M+, Calculated for C13H16BrF3N2O2S: 401.24. Used directly in the following step.

後処理

  1. extractionextracted with DCM three times
  2. washThe organic layer was washed with brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customThe crude was purified by silica gel chromatography
  6. custom40 g Grace column, 0-50% EtOAc-hexane in 20 min to give

出典と根拠

ORDレコード
ord-218f62e306ae42ec8df907bcbaff4743
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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