Tin tetrachloride → (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

HRID 422155Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 422155
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([S:9][CH2:10][C@@H:11]2[C@:20]3([CH3:21])[C@H:15]([C:16]([CH3:23])([CH3:22])[CH2:17][CH2:18][CH2:19]3)[CH2:14][CH2:13][C@@:12]2([CH3:25])O)[CH:6]=[CH:7][CH:8]=1.Cl[Sn](Cl)(Cl)Cl>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:6]([C@@:12]3([CH3:25])[C@H:11]([CH2:10][S:9]2)[C@:20]2([CH3:21])[C@H:15]([C:16]([CH3:23])([CH3:22])[CH2:17][CH2:18][CH2:19]2)[CH2:14][CH2:13]3)=[CH:7][CH:8]=1

Komponenten

4

Edukt 2

HCID 24287Tin tetrachlorideHCID 58294805(1R,2R,4aS,8aS)-1-{[(3-methoxyphenyl)sulfanyl]methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol

Produkt 1

HCID 53240551(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trieneAusbeute 46,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a solution of (1R,2R,4aS,8aS)-1-{[(3-methoxyphenyl)sulfanyl]methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (12b) (2.5 g, 6.9 mmol) in CH2Cl2 (70 mL), cooled to −78° C., a solution of SnCl4 (3.22 mL, 27.6 mmol) in CH2Cl2 (30 mL) was added dropwise. The mixture was stirred at −78° C. for 4 h. The reaction was quenched with water (100 mL), and the organic layer was separated, dried (Na2SO4), and concentrated. Purification by column chromatography on silica gel (Hexanes/toluene, 2:1) gave (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 51) (1.10 g, 46%) as a white solid. 1H NMR (CDCl3): δ 7.19 (d, 1H), 6.58 (m, 2H), 3.72 (s, 3H), 2.95 (q, 2H), 2.40 (m, 1H), 1.84-1.35 (m, 9H), 1.20 (s, 3H), 1.18-0.99 (m, 2H), 0.95 (s, 3H), 0.85 (s, 3H), 0.82 (s, 3H). (1R,10R,11S,16S)-3-Methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 52) (0.44 g, 19%) was also isolated as a white solid. 1H NMR (CDCl3): δ 6.96 (t, 1H), 6.67 (d, 1H), 6.56 (d, 1H), 3.78 (s, 3H), 3.32 (m, 1H), 2.82 (q, 2H), 1.82-1.40 (m, 7H), 1.38 (s, 3H), 1.35-0.98 (m, 3H), 0.92 (s, 3H), 0.95 (m, 1H), 0.87 (s, 3H), 0.83 (s, 3H).

Aufarbeitung

  1. customThe reaction was quenched with water (100 mL)
  2. customthe organic layer was separated
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customPurification by column chromatography on silica gel (Hexanes/toluene, 2:1)

Quellen und Nachweise

ORD-Eintrag
ord-11288067561d4f0aa5dc5748234ae8de
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08101605B2

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