Dimethyl Sulfide → HCID 57714161、化合物

HRID 81430

反応式

HRID 81430 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 57714153(R)-2-(Trityl-amino)-butyraldehydeHCID 178506895HCID 178506895、化合物

生成物 1

HCID 57714161HCID 57714161、化合物

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 Et2O (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 (R)-2-(trityl-amino)-butyraldehyde (1 g, 1 eq, 3.03 mmol) in Et2O (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 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 gradient column chromatography, eluted with hexane:ether (100:0→90:10) to afford the title compound as a colourless oil. Yield: 0.53 g (47%). (50% de 3S,4R: 50% de 3R,4R) 1H-NMR (d6-DMSO, 250 MHz): δ 0.44 (t, 3H, J=7.03 Hz, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 0.52 & 0.77 (2×d, 6H, J=6.48 Hz, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 0.79-1.13 (m, 2H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 1.72 (m, 1H, —NHCH(CH2CH3)CH(CH (CH3)2)OH), 2.11 (m, 1H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 2.77 (m, 1H, —NH CH(CH2CH3)CH(CH(CH3)2)OH), 2.99 (m, 1H, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 4.55 (d, 1H, J=5.21 Hz, —NHCH(CH2CH3)CH(CH(CH3)2)OH), 7.15-7.46 (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 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
  6. extractionThe reaction mixture was extracted with Et2O (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 gradient column chromatography
  11. washeluted with hexane:ether (100:0→90:10)

出典と根拠

ORDレコード
ord-17b3550dac424618af2ea1c8106e5a3e
出典データセット
uspto-grants-2014_09
特許番号
US08846696B2

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