Dimethyl Sulfide → (3RS,4S)-2-methyl-4-(trityl-amino)-hexan-3-ol

HRID 1432403ノート

反応式

HRID 1432403 の反応式
S(C)C.[CH:4]([Li])([CH3:6])[CH3:5].[C:8]([NH:27][C@@H:28]([CH2:31][CH3:32])[CH:29]=[O:30])([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[NH4+].[Cl-]>CCOCC>[CH3:5][CH:4]([CH:29]([OH:30])[C@@H:28]([NH:27][C:8]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)([C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH2:31][CH3:32])[CH3:6]

参加物

6

反応物 4

HCID 1068Dimethyl SulfideHCID 25517Ammonium ChlorideHCID 57452676(S)-2-(tritylamino)butanalHCID 178506895HCID 178506895、化合物

生成物 1

HCID 57714148(3RS,4S)-2-methyl-4-(trityl-amino)-hexan-3-ol

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

実験手順

To a stirred suspension of CuBr.SMe2 (1.37 g, 2.2 eq, 6.66 mmol) in ether (100 mL) under an argon atmosphere at −78° C., was added isopropyllithium (0.7 M in pentane, 17.29 mL, 4 eq, 12.1 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 (1 g, 1 eq, 3.03 mmol) in ether (25 mL) dropwise with stirring. The reaction mixture was stirred at this temperature for 1 h, then allowed to warm to −55° C. and stirred at this temperature for 3 h. 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 ether (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:ether (100:0→90:10) to afford the title compound as a colourless oil; Yield: 0.36 g (32%). (50% de 3R,4S, 50% de 3S,4S). 1H-NMR (d6-DMSO, 250 MHz): δ 0.44 (t, 3H, J=6.79 Hz, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 0.52+0.76 (2×d, 6H, J=6.63 Hz, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 0.80-1.15 (m, 2H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 1.70 (m, 1H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 2.10 (m, 1H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 2.76 (m, 1H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 2.99 (m, 1H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 4.55 (d, 1H, J=5.84 Hz, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 7.17-7.46 (m, 15H, 3×Bz).

後処理

  1. customwas recooled to −70° C., to which
  2. stirringThe reaction mixture was stirred at this temperature for 1 h
  3. temperatureto warm to −55° C.
  4. stirringstirred at this temperature for 3 h
  5. temperatureto warm to room temperature over 16 h The reaction mixture
  6. extractionwas extracted with ether (2×200 mL)
  7. washthe combined organic phase washed with brine (50 mL)
  8. dry with materialdried (MgSO4)
  9. customevaporated in vacuo
  10. customThe residue was purified by silica gel column chromatography
  11. washeluted with hexane:ether (100:0→90:10)

出典と根拠

ORDレコード
ord-f57d8d07287348ef82db6c167813f904
出典データセット
uspto-grants-2009_11
特許番号
US07612079B2

反応ノート

読み込み中…