Dimethyl Sulfide → (2r,3s)-3-(Tritylamino)pentan-2-ol

HRID 81427ノート

反応式

HRID 81427 の反応式
S(C)C.[CH3:4][Li].[C:6]([NH:25][C@@H:26]([CH2:29][CH3:30])[CH:27]=[O:28])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[NH4+].[Cl-]>CCOCC.CCCCCC>[C:6]([NH:25][C@@H:26]([CH2:29][CH3:30])[C@H:27]([OH:28])[CH3:4])([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

参加物

7

反応物 4

HCID 1068Dimethyl SulfideHCID 25517Ammonium ChlorideHCID 57452676(S)-2-(tritylamino)butanalHCID 178418348HCID 178418348、化合物

生成物 1

HCID 57433109(2r,3s)-3-(Tritylamino)pentan-2-ol

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒3 回HCID 8058Hexane溶媒

実験手順

To a stirred suspension of CuBr.SMe2 (2.74 g, 2.2 eq, 13.33 mmol) in ether (100 mL) under an argon atmosphere at −70° C., was added methyl lithium (1.6 M in ether, 15.13 mL, 4.0 eq, 24.21 mmol) dropwise and the solution allowed to warm to room temperature. The mixture was recooled to −70° C., to which was added a solution of (S)-2-(trityl-amino)-butyraldehyde (2 g, 1 eq, 6.05 mmol) in Et2O (25 mL) dropwise with stirring. The reaction mixture was stirred at this temperature for 2 h and then at −55° C. for 4 h, when TLC (hexane:Et2O; 80:20) indicated that the reaction had gone to completion. To the reaction mixture was added a saturated aqueous solution of NH4Cl (100 mL) and allowed to warm to room temperature over 16 h. The reaction mixture was extracted with Et2O (2×200 mL), and the combined organic phase washed with brine (50 mL), dried (MgSO4) and evaporated in vacuo. The residue was purified by silica gel column chromatography, eluted with hexane:Et2O (80:20) to afford the title compound as a light yellow oil. Yield: 1.37 g (66%). (80% de 2R,3S: 20% de 2S,3S). 1H-NMR (d6-DMSO, 250 MHz): δ 0.0.47 & 0.55 (2×t, J=7.50 & 7.26 Hz —NHCH(CH2CH3)CH(CH3)OH), 0.99-1.12 (m, 5H, —NHCH(CH2CH3)CH(CH3OH), 2.01 (m, 1H, —NHCH(CH2CH3)CH(CH3)OH), 3.22-3.43 (m, 1H, —NHCH(CH2CH3) CH(CH3)OH), 4.41 (d, 1H, J=3.31 Hz, —NHCH(CH2CH3)CH(CH3)OH), 7.14-7.56 (m, 15H, 3×Ph).

後処理

  1. customwas recooled to −70° C., to which
  2. stirringThe reaction mixture was stirred at this temperature for 2 h
  3. temperatureto warm to room temperature over 16 h
  4. extractionThe reaction mixture was extracted with Et2O (2×200 mL)
  5. washthe combined organic phase washed with brine (50 mL)
  6. dry with materialdried (MgSO4)
  7. customevaporated in vacuo
  8. customThe residue was purified by silica gel column chromatography
  9. washeluted with hexane:Et2O (80:20)

出典と根拠

ORDレコード
ord-536734aa5c69415aae9a292cbfb0529e
出典データセット
uspto-grants-2014_09
特許番号
US08846696B2

反応ノート

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