Dimethyl Sulfide → (2S,3R)-3-(trityl-amino)-pentan-2-ol

HRID 729564노트

반응식

HRID 729564 반응식
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

참가 물질

7

반응물 4

HCID 1068Dimethyl SulfideHCID 25517Ammonium ChlorideHCID 57714153(R)-2-(Trityl-amino)-butyraldehydeHCID 178418348HCID 178418348, 화합물

생성물 1

HCID 57714160(2S,3R)-3-(trityl-amino)-pentan-2-ol

시약·촉매·용매 2

HCID 3283Diethyl Ether용매3회HCID 8058Hexane용매

실험 절차

To a stirred suspension of CuBr.SMe2 (2.74 g, 2.2 eq, 13.33 mmol) in Et2O (100 mL) under an argon atmosphere at −70° C., was added methyllithium (1.6 M in Et2O, 16.6 mL, 4.4 eq, 26.56 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 (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, when TLC (hexane:ether; 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 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 (80:20) to afford the title compound as a light yellow oil. Yield: 1.91 g (91%). (80% de 2S,3R: 20% de 2R,3R). 1H-NMR (d6-DMSO, 250 MHz): δ 0.47 & 0.55 (2×t, J=7.43 & 7.27 Hz, —NHCH(CH2CH3)CH(CH3)OH), 0.99-1.12 (m, 5H, —NHCH(CH2CH3)CH(CH3)OH), 2.03 (m, 1H, —NHCH(CH2CH3)CH(CH3)OH), 3.32-3.51 (m, 1H, —NHCH(CH2CH3)CH(CH3)OH), 4.40 (d, 1H, J=3.79 Hz, —NHCH(CH2CH3)CH(CH3)OH), 7.14-7.51 (m, 15H, 3×Ph).

후처리

  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 ether (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:ether (80:20)

출처 및 근거

ORD 기록
ord-94525e022f56486bac757d9a780b898c
출처 데이터셋
uspto-grants-2009_09
특허 번호
US07582642B2

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