Ethyl diazoacetate → HCID 67360452, compound

HRID 404317Notes

Reaction equation

HRID 404317 reaction equation
[CH2:1]([O:8][C:9]1[N:14]=[CH:13][C:12]2[CH2:15][CH2:16][C:17](=[CH2:18])[C:11]=2[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+](=[CH:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[N-]>C(Cl)Cl.C([O-])(=O)C.[Rh+2].C([O-])(=O)C>[CH2:1]([O:8][C:9]1[N:14]=[CH:13][C:12]2[CH2:15][CH2:16][C:17]3([CH2:18][CH:21]3[C:22]([O:24][CH2:25][CH3:26])=[O:23])[C:11]=2[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetateHCID 57467583HCID 57467583, compound

Product 1

HCID 67360452HCID 67360452, compoundYield 36.9%

Reagents, catalysts & solvents 2

HCID 21674Acetic acid, rhodium(2+) saltCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
45 °C

Procedure

Compound H6.6 (50.0 mg, 211 μmol) and rhodium (ii) acetate, dimer (9.31 mg, 21.1 μmol) (commercially available from Sigma-Aldrich, St. Louis, Mo., USA) were mixed in 1.6 mL dry DCM. The resulting solution was refluxed at 45° C. for 10 minutes. Ethyl diazoacetate (26.2 μL, 253 μmol) (commercially available from Sigma-Aldrich, St. Louis, Mo., USA) was then added to the mixture very slowly. After 1 hour, the reaction was cooled to room temperature. The catalyst was then filtered off, and the solvent was concentrated down with silica gel. The product was purified by column chromatography to give H6.7 (25.1 mg, 36.9%). NMR confirmed that the product was the trans isomer. MS ESI (pos.) m/e: 324.2 (M+H)+. 1H NMR (500 MHz, DMSO-d6) δ ppm 7.55-7.60 (3H, m), 7.37-7.47 (4H, m), 4.90 (2H, d, J=3.7 Hz), 4.12 (2H, q, J=7.1 Hz), 2.92 (2H, d, J=19.3 Hz), 2.82 (1H, dd, J=8.6, 6.4 Hz), 2.31 (1H, dd, J=8.4, 5.0 Hz), 2.19 (2H, ddd, J=8.7, 6.8, 2.8 Hz), 1.36 (1H, dd, J=6.0, 5.5 Hz), 1.21 (3H, t, J=7.1 Hz).

Workup

  1. addition, USA) was then added to the mixture very slowly
  2. temperaturethe reaction was cooled to room temperature
  3. filtrationThe catalyst was then filtered off
  4. concentrationthe solvent was concentrated down with silica gel
  5. customThe product was purified by column chromatography

Sources & evidence

ORD record
ord-b5f8b5ee36ab4f1fbb00087d3aa42c0d
Source dataset
uspto-grants-2014_06
Patent number
US08748462B2

Reaction notes

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