Methyl 4-iodobenzoate → Methyl 4-[3-[[(1,1-dimethylethoxy)carbonyl]amino]-1-propyn-1-yl]benzoate

HRID 1264247Notes

Reaction equation

HRID 1264247 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7](I)=[CH:6][CH:5]=1.[CH2:12]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[C:13]#[CH:14]>N1CCCCC1.[Cu]I>[C:18]([O:17][C:16]([NH:15][CH2:12][C:13]#[C:14][C:7]1[CH:8]=[CH:9][C:4]([C:3]([O:2][CH3:1])=[O:11])=[CH:5][CH:6]=1)=[O:22])([CH3:21])([CH3:20])[CH3:19]

Participants

5

Reactant 2

HCID 69273Methyl 4-iodobenzoateHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamate

Product 1

HCID 18617679Methyl 4-[3-[[(1,1-dimethylethoxy)carbonyl]amino]-1-propyn-1-yl]benzoateYield 67%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8082PiperidineSolvent

Procedure

Methyl-4-iodobenzoate (1.5 g, 5.7 mmol) and t-butyl prop-2-ynylcarbamate (0.89 g, 5.7 mmol, reference example 82) are dissolved in piperidine (12 mL) and this solution purged with nitrogen. Copper(I) iodide (22 mg, 0.11 mmol) and dichlorobis(triphenylphosphine) palladium (40 mg, 0.057 mmol) is added and the mixture is stirred at R.T. After 2 hours, the solvent is removed in vacuo and the residue added to CH2Cl2 and washed with 1N HCl, water and brine, then dried over magnesium sulfate. The solvent is removed in vacuo and the residue purified by flash chromatography, eluting with 20% ethyl acetate/hexane to provide the title compound as a white solid (1.1 g, 67% yield): 1H NMR (300 MHz, CDCl3) d 7.98 (d, 2H), 7.48 (d, 2H), 4.79 (bs, 1H), 4.17 (d, 2H), 3.91 (s, 3H), 1.48 (s, 9H).

Workup

  1. customthis solution purged with nitrogen
  2. customthe solvent is removed in vacuo
  3. additionthe residue added to CH2Cl2
  4. washwashed with 1N HCl, water and brine
  5. dry with materialdried over magnesium sulfate
  6. customThe solvent is removed in vacuo
  7. customthe residue purified by flash chromatography
  8. washeluting with 20% ethyl acetate/hexane

Sources & evidence

ORD record
ord-e82b8e49f2804b8dbc00dedb8a5ffbbf
Source dataset
uspto-grants-2003_04
Patent number
US06541505B1

Reaction notes

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