Boron trifluoride etherate → (+/-)(1R*,2R*,5S*)-5-benzyloxy-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexanol

HRID 502931노트

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HRID 502931 반응식
[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([S:11][CH3:12])=[CH:7][CH:6]=1)(=[O:4])=[O:3].[Li]CCCC.B(F)(F)F.CCOCC.[CH2:27]([O:34][C@H:35]1[CH2:40][CH2:39][C@@H:38]2[O:41][C@@H:37]2[CH2:36]1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[NH4+].[Cl-]>C1COCC1.CCOC(C)=O>[CH2:27]([O:34][C@@H:35]1[CH2:36][C@@H:37]([OH:41])[C@H:38]([CH2:1][S:2]([C:5]2[CH:10]=[CH:9][C:8]([S:11][CH3:12])=[CH:7][CH:6]=2)(=[O:4])=[O:3])[CH2:39][CH2:40]1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

참가 물질

8

반응물 5

HCID 8000Boron trifluoride etherateHCID 25517Ammonium ChlorideHCID 44016291-Methanesulfonyl-4-methylsulfanyl-benzeneHCID 12827123HCID 12827123, 화합물HCID 178418339Butyllithium

생성물 1

HCID 68469915(+/-)(1R*,2R*,5S*)-5-benzyloxy-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexanol수율 80.3%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8857Ethyl Acetate용매

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온도
-78 °C

실험 절차

1-Methanesulfonyl-4-methylsulfanyl-benzene (3.25 g) was dissolved in THF (50 mL) and cooled to −78° C. prior to the addition of 1.6 M nBuLi (10 mL). After 0.5 h, BF3-Et2O (2.04 mL) was added followed by (±)(1S*,2R*,4S*)-4-(benzyloxy)-1,2-epoxycyclohexane (2.19 g) (Chini et al. J. Org. Chem. 1990, 55, 4265) in THF (20 mL). After an addition 1 h at −78° C., the solution was warmed to 0° C. After 2 h, the solution was cooled to −78° C. and saturated NH4Cl solution (aq) was added. The solution was warmed to rt and EtOAc was added. The organic layer was washed with brine, dried, filtered, and concentrated. Flash chromatography of the resulting residue gave (±)(1R*,2R*,5S*)-5-benzyloxy-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexanol (3.5 g) as the major product: 1H NMR (CDCl3, δppm, 300 mHz) 1.41 (m, 2H), 1.59 (m, 1H), 1.95 (m, 1H), 2.05-2.35 (m, 2H), 2.54 (s, 3H), 2.96 (dd, 1H), 3.64 (m, 2H), 3.81 (s, 1H), 4.48 (m, 2H), 7.3 (m, 7H), 7.82 (d, 2H).

후처리

  1. additionAfter an addition 1 h at −78° C.
  2. temperaturethe solution was warmed to 0° C
  3. waitAfter 2 h
  4. temperaturethe solution was cooled to −78° C.
  5. temperatureThe solution was warmed to rt
  6. washThe organic layer was washed with brine
  7. customdried
  8. filtrationfiltered
  9. concentrationconcentrated

출처 및 근거

ORD 기록
ord-8f023ca698ef4cc68bfb4ad201bcdd3e
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07776884B2

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