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

HRID 422132Notes

Reaction equation

[CH3:1][O:2][C:3]1[CH:4]=[C:5]([S:10][CH2:11][C@@H:12]2[C@:21]3([CH3:22])[C@H:16]([C:17]([CH3:24])([CH3:23])[CH2:18][CH2:19][CH2:20]3)[CH2:15][CH2:14][C@@:13]2([CH3:26])O)[CH:6]=[C:7]([CH3:9])[CH:8]=1.Cl[Sn](Cl)(Cl)Cl.O>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH3:9])[CH:6]=[C:5]2[C:4]=1[C@@:13]1([CH3:26])[C@H:12]([CH2:11][S:10]2)[C@:21]2([CH3:22])[C@H:16]([C:17]([CH3:24])([CH3:23])[CH2:18][CH2:19][CH2:20]2)[CH2:15][CH2:14]1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of (1R,2R,4aS,8aS)-1-{[(3-methoxy-5-methylphenyl)-sulfanyl]methyl}-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (13) (5.70 g, 15.1 mmol) in CH2Cl2 (300 mL) was added dropwise SnCl4 (1 M in CH2Cl2, 60 mL, 60 mmol) at −78° C. over 20 min. After complete addition, the reaction mixture was allowed to warm to 0° C. for 1 h. Water (50 mL) was added at 0° C. The organic layer was separated, dried (Na2SO4), and concentrated. Trituration with EtOAc (60 mL) gave (1R,10R,11S,16S)-3-methoxy-1,5,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 14) (1.44 g, batch 1) as a white solid. The filtrate was recrystallized to afford an additional batch (1.56 g, total yield 55%) as white crystals. 1H NMR (CDCl3): δ 6.52 (d, 1H), 6.38 (d, 1H), 3.78 (s, 3H), 3.30 (m, 1H), 2.84 (m, 1H), 2.76 (m, 1H), 2.20 (s, 3H), 1.84-1.40 (m, 8H), 1.38 (s, 3H), 1.34-1.00 (m, 3H), 0.95 (s, 3H), 0.86 (s, 3H), 0.86 (s, 3H). MS m/z 359 (C23H34OS+H+).

Workup

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

Sources & evidence

ORD record: ord-a7627dbc6925413cb09a77a71d482f87
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08101605B2

Reaction notes

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