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

HRID 502931ノート

反応式

HRID 502931 の反応式
[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

参加物

8

反応物 5

HCID 8000Boron trifluoride etherateHCID 25517Ammonium ChlorideHCID 44016291-Methanesulfonyl-4-methylsulfanyl-benzeneHCID 12827123HCID 12827123、化合物HCID 178418339Butyllithium

生成物 1

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

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-8f023ca698ef4cc68bfb4ad201bcdd3e
出典データセット
uspto-grants-2010_08
特許番号
US07776884B2

反応ノート

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