Aluminium lithium hydride → (2S,3S)-2,3-bis((2-methylallyl)oxy)butane-1,4-diol

HRID 1627039노트

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HRID 1627039 반응식
[CH3:1][C:2](=[CH2:20])[CH2:3][O:4][C@H:5]([C@@H:10]([O:15][CH2:16][C:17]([CH3:19])=[CH2:18])[C:11](OC)=[O:12])[C:6](OC)=[O:7].[H-].[H-].[H-].[H-].[Li+].[Al+3]>C1COCC1>[CH3:20][C:2](=[CH2:1])[CH2:3][O:4][C@H:5]([C@@H:10]([O:15][CH2:16][C:17]([CH3:19])=[CH2:18])[CH2:11][OH:12])[CH2:6][OH:7]

참가 물질

4

반응물 2

HCID 21226445Aluminium lithium hydrideHCID 86701304(2R,3R)-dimethyl 2,3-bis((2-methylallyl)oxy)succinate

생성물 1

HCID 86701305(2S,3S)-2,3-bis((2-methylallyl)oxy)butane-1,4-diol수율 92%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

To a solution of (2R,3R)-dimethyl 2,3-bis((2-methylallyl)oxy)succinate (14.7 g, 51.3 mmol) in THF (130 mL) at 0° C. was added slowly a 1.0 M solution of LAH in THF (257 mL, 257 mmol). The mixture was warmed to room temperature and stirred for 2 h, carefully quenched by the addition of EtOAc at 0° C., and then treated with a saturated aqueous solution of potassium sodium tartrate (Rochelle's salt). The phases were separated and the aqueous layer was extracted with EtOAc. The combined organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by flash chromatography (SiO2, hexanes/EtOAc gradient) to yield the title compound as a colorless oil (10.87 g, 92%): IR (neat) 3388, 2918, 2880, 1656, 1452, 1046 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.98 (s, 2H), 4.90 (s, 2H), 4.03 (s, 4H), 3.81 (d, J=11.7 Hz, 2H), 3.71 (d, J=11.9 Hz, 2H), 3.64-3.59 (m, 2H), 2.57-2.47 (m, 2H), 1.75 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 142.16, 112.85, 78.75, 74.52, 60.85, 19.68; HRMS-ESI (m/z) [M]+ calcd for C12H22O4, 230.1518; found, 230.1519.

후처리

  1. customcarefully quenched by the addition of EtOAc at 0° C.
  2. additiontreated with a saturated aqueous solution of potassium sodium tartrate (Rochelle's salt)
  3. customThe phases were separated
  4. extractionthe aqueous layer was extracted with EtOAc
  5. washThe combined organic phases were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography (SiO2, hexanes/EtOAc gradient)

출처 및 근거

ORD 기록
ord-5fdd8db4b5be4290b43e6e0a7e211c0d
출처 데이터셋
uspto-grants-2014_07
특허 번호
US08785479B2

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