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

HRID 1984267노트

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HRID 1984267 반응식
S(C)C.[C:4]([Li])([CH3:7])([CH3:6])[CH3:5].[C:9]([NH:28][C@H:29]([CH2:32][CH3:33])[CH:30]=[O:31])([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[NH4+].[Cl-]>CCOCC>[CH3:5][C:4]([CH3:7])([CH:30]([OH:31])[C@H:29]([NH:28][C:9]([C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)([C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH2:32][CH3:33])[CH3:6]

참가 물질

6

반응물 4

HCID 1068Dimethyl SulfideHCID 25517Ammonium ChlorideHCID 57714153(R)-2-(Trityl-amino)-butyraldehydeHCID 178418306HCID 178418306, 화합물

생성물 1

HCID 57714159(3RS,4R)-2,2-Dimethyl-4-(trityl-amino)-hexan-3-ol

시약·촉매·용매 1

HCID 3283Diethyl Ether용매2회

실험 절차

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 tert-butyllithium (1.5 M in pentane, 8.0 mL, 4 eq, 12.0 mmol) dropwise and the solution allowed to warn to room temperature. The mixture was recooled to −55° 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 stirning, 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 light yellow oil. Yield: 0.57 g (49%). (55% de 3S,4R: 45% de 3R,4R). 1H-NMR (d6-DMSO, 250 MHz): δ0.36 & 0.86 (2×t, 3H, J=7.42 Hz, —NH CH(CH2CH3)CH(C(CH3)3)OH), 0.57 & 0.71 (2×s, 9H, —NHCH(CH2CH3)CH (C(CH3)3)OH), 1.38-1.52 (m, 2H, —NHCH(CH2CH3)CH(C(CH3)3)OH), 1.99 (m, 1H, —NHCH(CH2CH3)CH(C(CH3)3)OH), 2.27 (m, 1H, —NHCH(CH2CH3)CH (C(CH3)3)OH), 2.95 (m, 1H, —NHCH(CH2CH3) CH(C(CH3)3)OH), 4.22 & 4.77 (2×d, 1H, J=4.42 5.21 Hz, —NHCH(CH2CH3) CH(C(CH3)3)OH), 7.14-7.52 (m, 15H, 3×Ph).

후처리

  1. customto warn to room temperature
  2. customwas recooled to −55° C., to which
  3. extractionThe reaction mixture was extracted with Et2O (2×200 mL)
  4. washthe combined organic phase washed with brine (50 mL)
  5. dry with materialdried (MgSO4)
  6. customevaporated in vacuo
  7. customThe residue was purified by silica gel gradient column chromatography
  8. washeluted with hexane:ether (100:0→90:10)

출처 및 근거

ORD 기록
ord-6c66fd913a90484f90ea87164ea73aa7
출처 데이터셋
uspto-grants-2009_06
특허 번호
US07544689B2

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