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

HRID 729565

반응식

HRID 729565 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 57452676(S)-2-(tritylamino)butanalHCID 178418348HCID 178418348, 화합물

생성물 1

HCID 57433109(2r,3s)-3-(Tritylamino)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 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): δ0.0.47 & 0.55 (2×t, J=7.50 & 7.26 Hz —NHCH(CH2CH3)CH(CH3)OH), 0.99-1.12 (m, 5H, —NHCH(CH2CH3)CH(CH3)OH), 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).

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 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)

출처 및 근거

ORD 기록
ord-166d9d5a8fbd40a1855a49c50fdd7aac
출처 데이터셋
uspto-grants-2009_09
특허 번호
US07582642B2

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