Triethylborane → (4-Acetoxy-6-fluoro-3-vinyl-naphthalen-2-yl)acetic acid methyl ester

HRID 238643Notes

Reaction equation

HRID 238643 reaction equation
[Cl-].[Cl-].[Cl-].[In+3].C([SiH](CC)CC)C.[CH3:12][O:13][C:14](=[O:33])[CH2:15][C:16]1[C:25]([C:26]#[CH:27])=[C:24]([O:28][C:29](=[O:31])[CH3:30])[C:23]2[C:18](=[CH:19][CH:20]=[C:21]([F:32])[CH:22]=2)[CH:17]=1.C(B(CC)CC)C>C(#N)C.O>[CH3:12][O:13][C:14](=[O:33])[CH2:15][C:16]1[C:25]([CH:26]=[CH2:27])=[C:24]([O:28][C:29](=[O:31])[CH3:30])[C:23]2[C:18](=[CH:19][CH:20]=[C:21]([F:32])[CH:22]=2)[CH:17]=1

Participants

7

Reactant 4

HCID 7357TriethylboraneHCID 12052TriethylsilaneHCID 159675indium(III)chlorideHCID 59326564(4-Acetoxy-3-ethynyl-6-fluoro-naphthalen-2-yl)-acetic acid methyl ester

Product 1

HCID 59326599(4-Acetoxy-6-fluoro-3-vinyl-naphthalen-2-yl)acetic acid methyl esterYield 62.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

A round-bottom flask (5 mL) charged with indium trichloride (88 mg, 0.40 mmol) was heated at 100° C. under reduced pressure for 1 h, and filled with nitrogen. A solution of triethylsilane (46 mg, 0.4 mmol) in acetonitrile (4 mL), which was cooled to 0° C., was added by means of syringe. After the mixture was stirred at 0° C. for 5 minutes, (4-acetoxy-3-ethynyl-6-fluoro-naphthalen-2-yl)-acetic acid methyl ester (60 mg, 0.20 mmol) and a solution of triethylborane (1M solution in tetrahydrofuran, 20 μL, 0.02 mmol) were added. The resulting mixture was stirred at 0° C. for 3 hours, then poured into water (10 mL), and extracted with ethyl acetate (10 mL×3). The organic layers were combined, dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash column (elution with 10% ethyl acetate in petroleum ether) to afford (4-acetoxy-6-fluoro-3-vinyl-naphthalen-2-yl)-acetic acid methyl ester (38 mg, 62.9%) as a pale solid.

Workup

  1. additionfilled with nitrogen
  2. additionwas added by means of syringe
  3. stirringThe resulting mixture was stirred at 0° C. for 3 hours
  4. extractionextracted with ethyl acetate (10 mL×3)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash column (elution with 10% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-68c93fd9f887436bac226ff87fe606ca
Source dataset
uspto-grants-2014_02
Patent number
US08642629B2

Reaction notes

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