Trimethylsulfonium iodide → HCID 86693878, compound

HRID 1186918Notes

Reaction equation

HRID 1186918 reaction equation
[I-].C[S+](C)C.[Li][CH2:7]CCC.[C:11]([Si:15]([O:18][CH2:19][C@@H:20]1[C@H:24]2[O:25][C:26]([CH3:29])([CH3:28])[O:27][C@H:23]2[C@@H:22]2[O:30][C@H:21]12)([CH3:17])[CH3:16])([CH3:14])([CH3:13])[CH3:12]>C1COCC1>[Si:15]([O:18][CH2:19][C@@H:20]1[C@H:24]2[O:25][C:26]([CH3:29])([CH3:28])[O:27][C@H:23]2[C@H:22]([OH:30])[C:21]1=[CH2:7])([C:11]([CH3:14])([CH3:12])[CH3:13])([CH3:17])[CH3:16]

Participants

5

Reactant 3

HCID 75127Trimethylsulfonium iodideHCID 86693879HCID 86693879, compoundHCID 178418339Butyllithium

Product 1

HCID 86693878HCID 86693878, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a −10° C. suspension of trimethylsulfonium iodide (30 g, 149.5 mmol) in THF (150 mL) was added n-BuLi 2.5 M hexane solution (46.0 mL, 83.0 mmol). After 30 min, epoxide (10) (5.0 g, 16.6 mmol) in THF (20 mL) was introduced and the reaction slowly allowed to warm to 0° C. over 1 h; the mixture was then stirred at ambient temperature for 2 hr. The reaction was quenched with water and extracted with ethyl acetate (50 mL×2). The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated under vacuum. The residues were purified on silica gel column chromatography (10% EtOAc/Hexane) to give allylic alcohol 11 (4 g, 80%) as an oil. [α]22D − 20.35° (c 2.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ 5.31 (s, 1H), 5.11 (s, 1H), 4.52 (d, J=6 Hz, 1H), 4.32-4.31 (m, 1H), 4.13-4.11 (m, 1H), 3.81-3.79 (m, 2H), 3.62-3.60 (m, 1H), 3.91-3.90 (m, 1H,), 2.62 (br, 1H), 1.30 (s, 3H), 1.20 (s, 3H), 0.80 (m, 9H), 0.013-0.006 (m, 6H); 13C NMR (125 MHz, CDCl3) δ 157.9, 115.9, 92.6, 88.8, 84.1, 72.4, 59.0, 32.6, 31.5, 30.4, 24.0, 0.05; HR-MS Calcd. For (C16H30O4Si+H)+ 315.1913, found 315.1892.

Workup

  1. customthe reaction
  2. customThe reaction was quenched with water
  3. extractionextracted with ethyl acetate (50 mL×2)
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe residues were purified on silica gel column chromatography (10% EtOAc/Hexane)

Sources & evidence

ORD record
ord-62265e404c8a454e89af4abb2fcdc21b
Source dataset
uspto-grants-2014_03
Patent number
US08673926B2

Reaction notes

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