Dichloromethane → (1R,10R,11S,16S)-1,11,15,15-tetramethyl-3,5-bis(propan-2-yloxy)-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

HRID 422152ノート

反応式

HRID 422152 の反応式
[CH3:1][CH:2]([O:4][C:5]1[CH:6]=[C:7]([CH:25]=[C:26]([O:28][CH:29]([CH3:31])[CH3:30])[CH:27]=1)[O:8][CH2:9][C@@H:10]1[C@:19]2([CH3:20])[C@H:14]([C:15]([CH3:22])(C)[CH2:16][CH2:17][CH2:18]2)[CH2:13][CH2:12][C@@:11]1([CH3:24])O)[CH3:3].Cl[Sn](Cl)(Cl)Cl.[CH2:37](Cl)Cl>>[CH3:24][C@@:11]12[CH2:12][CH2:13][C@@H:14]3[C@:15]([CH3:22])([CH2:16][CH2:17][CH2:18][C:19]3([CH3:20])[CH3:37])[C@H:10]1[CH2:9][O:8][C:7]1[C:25]2=[C:26]([O:28][CH:29]([CH3:30])[CH3:31])[CH:27]=[C:5]([O:4][CH:2]([CH3:3])[CH3:1])[CH:6]=1

参加物

4

反応物 3

HCID 6344Dichloromethane2 回HCID 24287Tin tetrachlorideHCID 58294796(1S,2R,4aS,8aS)-1-[3,5-bis(propan-2-yloxy)phenoxymethyl]-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol

生成物 1

HCID 53240455(1R,10R,11S,16S)-1,11,15,15-tetramethyl-3,5-bis(propan-2-yloxy)-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene収率 23%

反応条件

温度
-78 °C

実験手順

To a solution of (1S,2R,4aS,8aS)-1-[3,5-bis(propan-2-yloxy)phenoxy-methyl]-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (48) (0.90 g, 2.1 mmol) in CH2Cl2 (20 mL), cooled to −78° C., a solution of SnCl4 (0.97 mL, 8.3 mmol) in CH2Cl2 (10 mL) was added dropwise. The temperature was maintained at −78° C. for 4 h, after which the reaction mixture was allowed to warm to room temperature overnight. The reaction was quenched with water (50 mL). The organic layer was separated, dried (Na2SO4) and concentrated. Purification by column chromatography on silica gel (Hexanes/toluene, 1:1) gave (1R,10R,11S,16S)-1,11,15,15-tetramethyl-3,5-bis(propan-2-yloxy)-8-oxatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 49) (0.20 g, 23%) as a tan solid. 1H NMR (CDCl3): δ 5.95 (d, 1H), 5.87 (d, 1H), 4.50 (m, 1H), 4.40 (m, 1H), 4.22 (m, 1H), 3.95 (t, 1H), 3.10 (m, 1H) 1.78-1.40 (m, 7H), 1.37 (m, 15H), 1.25-1.00 (m, 4H) 0.92 (s, 3H), 0.87 (s, 3H), 0.82 (s, 3H).

後処理

  1. temperatureto warm to room temperature overnight
  2. customThe reaction was quenched with water (50 mL)
  3. customThe organic layer was separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customPurification by column chromatography on silica gel (Hexanes/toluene, 1:1)

出典と根拠

ORDレコード
ord-7b3ccf4c9a7a4833b1667f304395cf8f
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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