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 422152Notes

Reaction equation

HRID 422152 reaction equation
[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

Participants

4

Reactant 3

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

Product 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-trieneYield 23%

Conditions

Temperature
-78 °C

Procedure

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).

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/toluene, 1:1)

Sources & evidence

ORD record
ord-7b3ccf4c9a7a4833b1667f304395cf8f
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

Loading…