Triphenylphosphine → 1-Tert-butoxycarbonyl-4-(3-chlorophenyl)-2(s)-[2-(2-cyano-5-methoxycarbonylphenoxy)ethyl]-5-oxo-piperazine

HRID 379027Notes

Reaction equation

HRID 379027 reaction equation
[C:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][C:4]=1[OH:13])#[N:2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:33]([O:37][C:38]([N:40]1[CH2:45][C:44](=[O:46])[N:43]([C:47]2[CH:52]=[CH:51][CH:50]=[C:49]([Cl:53])[CH:48]=2)[CH2:42][C@@H:41]1[CH2:54][CH2:55]O)=[O:39])([CH3:36])([CH3:35])[CH3:34].CCOC(/N=N/C(OCC)=O)=O>C1COCC1.CCCCCC.CCOC(C)=O>[C:33]([O:37][C:38]([N:40]1[CH2:45][C:44](=[O:46])[N:43]([C:47]2[CH:52]=[CH:51][CH:50]=[C:49]([Cl:53])[CH:48]=2)[CH2:42][C@@H:41]1[CH2:54][CH2:55][O:13][C:4]1[CH:5]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:11]=[CH:12][C:3]=1[C:1]#[N:2])=[O:39])([CH3:36])([CH3:35])[CH3:34]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 16641129Methyl 4-cyano-3-hydroxybenzoateHCID 20691434(S)-4-(tert-butoxycarbonyl)-1-(3-chlorophenyl)-5-(2-hydroxyethyl)piperazin-2-one

Product 1

HCID 206914331-Tert-butoxycarbonyl-4-(3-chlorophenyl)-2(s)-[2-(2-cyano-5-methoxycarbonylphenoxy)ethyl]-5-oxo-piperazine

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a solution of 250 mg of methyl 4-cyano-3-hydroxybenzoate (1.42 mmol), as described in Example 4, Step C, and PPh3 (465 mg, 1.77 mmol) in THF (10 mL) was added dropwise a solution of the alcohol from Step E above (503 mg, 1.42 mmol) and DEAD (0.28 mL, 1.77 mmol) in THF (5 mL). After stirring for 16 hr, the solution was concentrated in vacuo and the residue taken up in EtOAc. This was then washed with 10% citric acid solution, saturated NaHCO3 solution, brine and dried over MgSO4. Filtration and removal of the solvent afforded an oil. Column chromatography (silica gel; hexane:EtOAc 4:1) afforded the title compound as a clear oil.

Workup

  1. concentrationthe solution was concentrated in vacuo
  2. washThis was then washed with 10% citric acid solution, saturated NaHCO3 solution, brine
  3. dry with materialdried over MgSO4
  4. filtrationFiltration and removal of the solvent
  5. customafforded an oil

Sources & evidence

ORD record
ord-803ee359b31a40149f696cffb6d8027a
Source dataset
uspto-grants-2001_10
Patent number
US06297239B1

Reaction notes

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