Fluoride Ion → 6-(2-Cyclopentyl-2-hydroxy-but-3-ynyl)-2,2-dimethyl-[1,3]dioxin-4-one

HRID 2387006Notes

Reaction equation

HRID 2387006 reaction equation
[CH:1]1([C:6]([OH:23])([C:17]#[C:18][Si](C)(C)C)[CH2:7][C:8]2[O:13][C:12]([CH3:15])([CH3:14])[O:11][C:10](=[O:16])[CH:9]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1.[F-]>CO>[CH:1]1([C:6]([OH:23])([C:17]#[CH:18])[CH2:7][C:8]2[O:13][C:12]([CH3:15])([CH3:14])[O:11][C:10](=[O:16])[CH:9]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

4

Reactant 2

HCID 28179Fluoride IonHCID 224997936-(2-Cyclopentyl-2-hydroxy-4-trimethylsilanyl-but-3-ynyl)-2,2-dimethyl-[1,3]dioxin-4-one

Product 1

HCID 224998026-(2-Cyclopentyl-2-hydroxy-but-3-ynyl)-2,2-dimethyl-[1,3]dioxin-4-oneYield 54.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of crude 6-[2-cyclopentyl-2-hydroxy-4-(trimethylsilyl)but-3-yn-1-yl]-2,2-dimethyl-4H-1,3-dioxin-4-one (25 mmol), ceasium fluoride (7.6 g, 50 mmol) dissolved in MeOH (75 mL) was stirred over night. The solvent was removed and the residue was diluted with EtOAc, washed with 0.5 N citric acid, 1 N NaHCO3, brine, dried over MgSO4 and concentrated. Purification by flash column chromatography (20% to 30% EtOAc in hexanes) gave the product (3.6 g, 54%). 1H NMR (300 MHz, CDCl3) □: 1.45-1.80 (m, 8 H), 1.72 (s, 3H), 1.74 (s, 3 H), 2.13-2.18 (m, 1 H), 2.49 (s, 1 H), 2.56 (s, 1 H), 2.58 (s, 2 H), 5.43 (s, 1 H).

Workup

  1. customThe solvent was removed
  2. additionthe residue was diluted with EtOAc
  3. washwashed with 0.5 N citric acid, 1 N NaHCO3, brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customPurification by flash column chromatography (20% to 30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-cded3d17fe3548e2b5dc73a52dd6e7fa
Source dataset
uspto-grants-2012_09
Patent number
US08268835B2

Reaction notes

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