Tin tetrachloride → (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

HRID 422146Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 422146
[CH3:1][O:2][C:3]1[CH:25]=[C:24]([O:26][CH3:27])[CH:23]=[CH:22][C:4]=1[O:5][CH2:6][C@@H:7]1[C@:16]2([CH3:17])[C@H:11]([C:12]([CH3:19])([CH3:18])[CH2:13][CH2:14][CH2:15]2)[CH2:10][CH2:9][C@@:8]1([CH3:21])O.Cl[Sn](Cl)(Cl)Cl>C(Cl)Cl>[CH3:27][O:26][C:24]1[CH:23]=[C:22]2[C:4](=[C:3]([O:2][CH3:1])[CH:25]=1)[O:5][CH2:6][C@H:7]1[C@@:8]2([CH3:21])[CH2:9][CH2:10][C@@H:11]2[C@:16]1([CH3:17])[CH2:15][CH2:14][CH2:13][C:12]2([CH3:19])[CH3:18]

Komponenten

4

Edukt 2

HCID 24287Tin tetrachlorideHCID 58294797(1S,2R,4aS,8aS)-1-(2,4-dimethoxyphenoxymethyl)-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol

Produkt 1

HCID 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-trieneAusbeute 80,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a solution of (1S,2R,4aS,8aS)-1-(2,4-dimethoxyphenoxymethyl)-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (41) (0.90 g, 2.4 mmol) in CH2Cl2 (20 mL), cooled to −78° C., a solution of SnCl4 (1.11 mL, 9.56 mmol) in CH2Cl2 (10 mL) was added dropwise. The temperature was maintained at −78° C. for 4 h then the 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/EtOAc, 4:1) gave (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, 80%) as a viscous yellow oil. 1H NMR (CDCl3): δ 6.33 (d, 1H), 6.00 (d, 1H), 4.45 (m, 1H), 4.18 (t, 1H), 3.83 (s, 3H), 3.75 (s, 3H), 2.25 (m, 1H) 1.80-1.38 (m, 7H), 1.35 (s, 3H), 1.25-1.00 (m, 4H) 0.92 (s, 3H), 0.87 (s, 3H), 0.82 (s, 3H).

Aufarbeitung

  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/EtOAc, 4:1)

Quellen und Nachweise

ORD-Eintrag
ord-9bfff9190c184a3b95c702bf9843ded2
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08101605B2

Notizen zur Reaktion

Wird geladen…