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 422166Notes

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

Conditions

Temperature: -78 °C

Procedure

A solution of (1R,2R,4aS,8aS)-1-{[(3-methoxyphenyl)sulfanyl]-methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (13-1) (1.2 g, 3.2 mmol) in CH2Cl2 (85 mL) was cooled to −78° C. under N2. To the mixture, a solution of SnCl4 (1.5 mL) in CH2Cl2 (15 mL) was added dropwise. The mixture was stirred at −78° C. for 3 h. The dry ice bath was removed and stirring at room temperature continued for 2 h. The reaction mixture was quenched with water and the organic layer was separated and concentrated to dryness. The crude product was purified by flash chromatography on silica gel (Hexanes/Toluene, 2:1) to yield (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 (51) (1.0 g, 93% yield) as a white solid. Regioisomer (52) was also obtained as shown in Example 26.

Workup

customThe dry ice bath was removed
stirringstirring at room temperature
waitcontinued for 2 h
customThe reaction mixture was quenched with water
customthe organic layer was separated
concentrationconcentrated to dryness
customThe crude product was purified by flash chromatography on silica gel (Hexanes/Toluene, 2:1)

Sources & evidence

ORD record: ord-3bf4626f06a4427fabe9d125ce1f6ec6
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08101605B2

Reaction notes

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