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 422155Notes

Reaction equation

HRID 422155 reaction equation
[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

Participants

4

Reactant 2

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

Product 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-trieneYield 46.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-11288067561d4f0aa5dc5748234ae8de
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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