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 422146Notes

Reaction equation

HRID 422146 reaction equation
[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]

Participants

4

Reactant 2

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

Product 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-trieneYield 80.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-9bfff9190c184a3b95c702bf9843ded2
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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