Boron tribromide → (1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-4,6-diol

HRID 422147ノート

反応式

HRID 422147 の反応式
C[O:2][C:3]1[CH:4]=[C:5]2[C:18](=[C:19]([O:21]C)[CH:20]=1)[O:17][CH2:16][C@H:15]1[C@@:6]2([CH3:26])[CH2:7][CH2:8][C@@H:9]2[C@:14]1([CH3:23])[CH2:13][CH2:12][CH2:11][C:10]2([CH3:25])[CH3:24].B(Br)(Br)Br>C(Cl)Cl>[CH3:26][C@@:6]12[CH2:7][CH2:8][C@@H:9]3[C@:14]([CH3:23])([CH2:13][CH2:12][CH2:11][C:10]3([CH3:24])[CH3:25])[C@H:15]1[CH2:16][O:17][C:18]1[C:5]2=[CH:4][C:3]([OH:2])=[CH:20][C:19]=1[OH:21]

参加物

4

反応物 2

HCID 25134Boron tribromideHCID 53240452(1R,10R,11S,16S)-4,6-dimethoxy-1,11,15,15-tetramethyl-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

生成物 1

HCID 53240454(1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-4,6-diol

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of (1R,10R,11S,16S)-4,6-dimethoxy-1,11,15,15-tetramethyl-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 42) (0.69 g, 1.9 mmol) in CH2Cl2 (20 mL), cooled to 0° C., and a BBr3 solution (7.3 mL, 1 M in CH2Cl2, 7.3 mmol) was added dropwise. The ice bath was removed and the reaction was stirred at room temperature for 6 h. The reaction was quenched with MeOH (20 mL) and concentrated. The quenching and concentration steps were repeated six times. Purification by column chromatography on silica gel (Hexanes/EtOAc, 4:1) gave (1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-4,6-diol (Compound No. 43) (0.42 g, 66%) as a pale pink solid. 1H NMR (CDCl3): δ 6.28 (d, 1H), 6.17 (d, 1H), 5.48 (br s, 1H), 4.40 (m, 1H), 4.25 (br s, 1H), 4.15 (t, 1H), 2.20 (m, 1H), 1.80-1.35 (m, 7H), 1.28 (s, 3H), 1.25-1.00 (m, 4H), 0.92 (s, 3H), 0.88 (s, 3H), 0.82 (s, 3H). MS m/z 331 (C21H30O3+H+).

後処理

  1. customThe ice bath was removed
  2. customThe reaction was quenched with MeOH (20 mL)
  3. concentrationconcentrated
  4. concentrationThe quenching and concentration steps
  5. customPurification by column chromatography on silica gel (Hexanes/EtOAc, 4:1)

出典と根拠

ORDレコード
ord-c0077aaa574844df8631cba9d402772a
出典データセット
uspto-grants-2012_01
特許番号
US08101605B2

反応ノート

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