Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → HCID 86603705, compound

HRID 226396Notes

Reaction equation

HRID 226396 reaction equation
O[CH2:2][C:3]1[CH:4]=[CH:5][C:6]([NH:9][C@@H:10]2[CH2:15][CH2:14][CH2:13][N:12]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:11]2)=[N:7][CH:8]=1.[C:23]([CH:28]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:25][CH2:26][CH3:27])=[O:24]>O1CCOCC1.[O-2].[Mn+4].[O-2]>[CH2:26]([O:25][C:23](=[O:24])/[CH:28]=[CH:2]/[C:3]1[CH:4]=[CH:5][C:6]([NH:9][C@@H:10]2[CH2:15][CH2:14][CH2:13][N:12]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:11]2)=[N:7][CH:8]=1)[CH3:27]

Participants

5

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 86603706HCID 86603706, compound

Product 1

HCID 86603705HCID 86603705, compoundYield 89.3%

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of tert-butyl (3R)-3-{[5-(hydroxymethyl)-2-pyridinyl]amino}-1-piperidinecarboxylate (3.65 g, 11.9 mmol) in dioxane (50 mL) was added manganese(IV) oxide (7.7 g, 89 mmol) and (carbethoxymethylene)triphenylphosphorane (6.2 g, 17.8 mmol). After stirring for 18 hrs at 60° C., a resulting precipitate was filtered and the filtrate was evaporated in vacuo and the residue was partitioned between water and EtOAc. The organic layer was separated, washed water and brine, dried over magnesium sulfate, and evaporated in vacuo. The residue was purified by silica gel column chromatography (CHCl3/methanol=95/5)to give tert-butyl (3R)-3-({5-[(1E)-3-ethoxy-3-oxo-1-propen-1-yl]-2-pyridinyl}amino)-1-piperidinecarboxylate (3.99 g, 89%).

Workup

  1. filtrationa resulting precipitate was filtered
  2. customthe filtrate was evaporated in vacuo
  3. customthe residue was partitioned between water and EtOAc
  4. customThe organic layer was separated
  5. washwashed water and brine
  6. dry with materialdried over magnesium sulfate
  7. customevaporated in vacuo
  8. customThe residue was purified by silica gel column chromatography (CHCl3/methanol=95/5)to

Sources & evidence

ORD record
ord-9af851f3e68942a2a0a52be966159663
Source dataset
uspto-grants-2009_07
Patent number
US07557127B2

Reaction notes

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