Propargyl alcohol → HCID 67373277, compound

HRID 1805912Notes

Reaction equation

HRID 1805912 reaction equation
C(N(CC)CC)C.[C:8]([O:11][C:12]1[C:21]([CH3:22])=[CH:20][C:19](I)=[CH:18][C:13]=1[C:14]([O:16][CH3:17])=[O:15])(=[O:10])[CH3:9].[CH2:24]([OH:27])[C:25]#[CH:26]>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:8]([O:11][C:12]1[C:21]([CH3:22])=[CH:20][C:19]([C:26]#[C:25][CH2:24][OH:27])=[CH:18][C:13]=1[C:14]([O:16][CH3:17])=[O:15])(=[O:10])[CH3:9]

Participants

7

Reactant 3

HCID 7859Propargyl alcoholHCID 8471TriethylamineHCID 67374420HCID 67374420, compound

Product 1

HCID 67373277HCID 67373277, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Triethylamine (0.943 mL, 6.76 mmol) and bis(triphenylphosphine)palladium(II) chloride (0.092 g, 0.132 mmol) were added to a mixture of methyl 2-(acetyloxy)-5-iodo-3-methylbenzoate (1.0 g, 2.99 mmol) and propargyl alcohol (0.161 mL, 2.69 mmol) in THF (20 mL) at room temperature, and then copper (I) iodide (0.053 g, 0.278 mmol) was added. The resulting mixture was stirred at room temperature for 18 h. The reaction was quenched with water (20 mL) and extracted with EtOAc (3×30 mL). The combined organic extracts were washed with water (50 mL), brine (40 mL), dried (MgSO4), and concentrated in vacuo to give the crude product. This was purified by flash chromatography (Si, 0-20% EtOAc in hexanes over 30 min) to afford methyl 2-(acetyloxy)-5-(3-hydroxyprop-1-yn-1-yl)-3-methylbenzoate, as a yellow solid. 1H NMR (500 MHz, CHCl3): δ 7.97 (s, 1 H); 7.53 (s, 1 H); 4.91 (s, 2 H); 3.88 (s, 3 H); 2.22 (s, 3 H); 2.16 (s, 3 H).

Workup

  1. customThe reaction was quenched with water (20 mL)
  2. extractionextracted with EtOAc (3×30 mL)
  3. washThe combined organic extracts were washed with water (50 mL), brine (40 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customto give the crude product
  7. customThis was purified by flash chromatography (Si, 0-20% EtOAc in hexanes over 30 min)

Sources & evidence

ORD record
ord-ce89db69b00d46b4814dcec5a56ca816
Source dataset
uspto-grants-2013_01
Patent number
US08354454B2

Reaction notes

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