Benzoic Acid → HCID 67193470, compound

HRID 547778Notes

Reaction equation

HRID 547778 reaction equation
[CH2:1]([N:8]1[CH2:13][C@H:12]([O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[CH2:11][C@@H:10]([OH:22])[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N(C(OCC)=O)=NC(OCC)=O.C(O)(=O)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCCC1>[CH2:1]([N:8]1[CH2:13][C@H:12]([O:14][Si:15]([C:18]([CH3:20])([CH3:19])[CH3:21])([CH3:16])[CH3:17])[CH2:11][C@H:10]([OH:22])[CH2:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 5

HCID 243Benzoic AcidHCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 11220958HCID 11220958, compound

Product 1

HCID 67193470HCID 67193470, compoundYield 6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 1.8 g (5.6 mmol) (3R,5R)-1-benzyl-5-(tert-butyl-dimethyl-silanyloxy)-piperidin-3-ol in 50 ml tetrahydrofuran were added at 0° C. 0.97 ml (6.2 mmol) diethyl azodicarboxylate and 0.75 g (6.2 mmol) benzoic acid. The reaction mixture was cooled to 0° C., followed by addition of 1.6 g (6.2 mmol) triphenylphosphine. The reaction mixture was stirred at 0° C. for 6 h. Addition of a saturated sodium carbonate solution was followed by extraction with three portions of tert-butyl methyl ether. The combined organic layers were washed with saturated sodium carbonate solution and brine, dried over sodium sulfate, concentrated in vacuo and purified by flash chromatography. The residue was dissolved in a mixture of 50 ml dioxane and 18 ml 1 N aqueous sodium hydroxide solution. After stirring at 70° C. for 5 h the reaction mixture was diluted with tert-butyl methyl ether. The layers were separated and the organic layer was washed with a saturation aqueous sodium carbonate solution. The combined aqueous layers were extracted with two portions of tert-butyl methyl ether. The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. Flash chromatography gave 0.1 g (6%) of the title compound as a light brown oil.

Workup

  1. extractionwas followed by extraction with three portions of tert-butyl methyl ether
  2. washThe combined organic layers were washed with saturated sodium carbonate solution and brine
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. custompurified by flash chromatography
  6. dissolutionThe residue was dissolved in a mixture of 50 ml dioxane and 18 ml 1 N aqueous sodium hydroxide solution
  7. stirringAfter stirring at 70° C. for 5 h the reaction mixture
  8. additionwas diluted with tert-butyl methyl ether
  9. customThe layers were separated
  10. washthe organic layer was washed with a saturation aqueous sodium carbonate solution
  11. extractionThe combined aqueous layers were extracted with two portions of tert-butyl methyl ether
  12. washThe combined organic layers were washed with brine
  13. dry with materialdried over sodium sulfate
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-03ab432b2d54429989125786a9d3ba08
Source dataset
uspto-grants-2011_05
Patent number
US07939533B2

Reaction notes

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