Ethylenediamine → (Z)-7-[2-Oxo-6-((E)-3-oxo-4-phenyl-but-1-enyl)-piperidin-1-yl]-hept-5-enoic acid methyl ester

HRID 352417Notes

Reaction equation

HRID 352417 reaction equation
[BH4-].[Na+].C(N)CN.[CH3:7][O:8][C:9](=[O:34])[CH2:10][CH2:11][CH2:12][C:13]#[C:14][CH2:15][N:16]1[CH:21](/[CH:22]=[CH:23]/[C:24](=[O:32])[CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:20][CH2:19][CH2:18][C:17]1=[O:33].[H][H]>C(O)C.[Ni](Cl)Cl>[CH3:7][O:8][C:9](=[O:34])[CH2:10][CH2:11][CH2:12]/[CH:13]=[CH:14]\[CH2:15][N:16]1[CH:21](/[CH:22]=[CH:23]/[C:24](=[O:32])[CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:20][CH2:19][CH2:18][C:17]1=[O:33]

Participants

7

Reactant 4

HCID 3301EthylenediamineHCID 4311764Sodium borohydrideHCID 104749617-[2-Oxo-6-((E)-3-oxo-4-phenyl-but-1-enyl)-piperidin-1-yl]-hept-5-ynoic acid methyl esterHCID 178418361HCID 178418361, compound

Product 1

HCID 10045505(Z)-7-[2-Oxo-6-((E)-3-oxo-4-phenyl-but-1-enyl)-piperidin-1-yl]-hept-5-enoic acid methyl esterYield 73%

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 702EthanolSolvent2×

Procedure

A round bottom flask was charged with nickel (II) chloride (68 mg, 0.52 mmol) and sodium borohydride (9.9 mg, 0.26 mmol), then 95% ethanol (1.0 mL) was added. The mixture immediately turned black. After 15 min at rt, ethylene diamine (56 μL, 0.84 mmol) was added. After another 15 min at rt, 7-[2-oxo-6-((E)-3-oxo-4-phenyl-but-1-enyl)-piperidin-1-yl]-hept-5-ynoic acid methyl ester (40 mg, 0.10 mmol) in 95% ethanol (1.0 mL) was added via cannula. A hydrogen atmosphere was established by evacuating and refilling with hydrogen (3×) and the reaction mixture was stirred under a balloon of hydrogen for 18 h. The reaction mixture was filtered through celite, washing with ethanol, and the filtrate was concentrated in vacuo. Purification of the resulting residue by flash column chromatography (CH2Cl2→30% EtOAc/CH2Cl2, gradient) afforded 28 mg (70%) of the title compound.

Workup

  1. waitAfter another 15 min at rt
  2. customby evacuating
  3. filtrationThe reaction mixture was filtered through celite
  4. washwashing with ethanol
  5. concentrationthe filtrate was concentrated in vacuo
  6. customPurification of the resulting residue by flash column chromatography (CH2Cl2→30% EtOAc/CH2Cl2, gradient)

Sources & evidence

ORD record
ord-1d2b669034484327aa8f234c20ef9434
Source dataset
uspto-grants-2004_06
Patent number
US06747037B1

Reaction notes

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