Water → (1R,10R,11S,16S)-3,5-dimethoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

HRID 422135Notes

Reaction equation

[CH3:1][O:2][C:3]1[CH:4]=[C:5]([S:11][CH2:12][C@@H:13]2[C@:22]3([CH3:23])[C@H:17]([C:18]([CH3:25])([CH3:24])[CH2:19][CH2:20][CH2:21]3)[CH2:16][CH2:15][C@@:14]2([CH3:27])O)[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1.Cl[Sn](Cl)(Cl)Cl.O>C(Cl)Cl>[CH3:10][O:9][C:7]1[CH:8]=[C:3]([O:2][CH3:1])[CH:4]=[C:5]2[C:6]=1[C@@:14]1([CH3:27])[C@H:13]([CH2:12][S:11]2)[C@:22]2([CH3:23])[C@H:17]([C:18]([CH3:24])([CH3:25])[CH2:19][CH2:20][CH2:21]2)[CH2:16][CH2:15]1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of (1R,2R,4aS,8aS)-1-{[(3,5-dimethoxyphenyl)sulfanyl]-methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (21) (1.0 g, 2.55 mmol) in CH2Cl2 (50 mL) was added dropwise SnCl4 (1 M in CH2Cl2, 10.2 mL, 10.19 mmol) at −78° C. over 5 min. After complete addition, the reaction mixture was allowed to warm to 0° C. for 1 h, then room temperature for 2 h. Water (20 mL) was added at room temperature followed by CH2Cl2 (50 mL). The organic layer was separated, dried (Na2SO4), and concentrated. Trituration with MeOH gave (1R,10R,11S,16S)-3,5-dimethoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 22) (0.77 g, 81%) as a white solid. 1H NMR (CDCl3): δ 6.22 (d, 1H), 6.18 (d, 1H), 3.78 (s, 3H), 3.78 (s, 3H), 3.25 (m, 1H), 2.90 (m, 1H), 2.78 (m, 1H), 1.84-1.38 (m, 7H), 1.37 (s, 3H), 1.36-1.00 (m, 3H), 0.95 (s, 3H), 0.90 (m, 1H), 0.85 (s, 3H), 0.85 (s, 3H). MS m/z 375 (C23H34O2S+H+).

Workup

additionAfter complete addition
customThe organic layer was separated
dry with materialdried (Na2SO4)
concentrationconcentrated

Sources & evidence

ORD record: ord-260dbc82fb9645e895fd917b31e4b70f
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08101605B2

Reaction notes

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