Imidazole → HCID 86757593, compound

HRID 429295Notes

Reaction equation

HRID 429295 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][C@H:12]1[C@H:24](O)[CH3:25])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH:27]1C=CN=C1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/[N:56]=[N:57]/C(OCC)=O)=O>C1(C)C=CC=CC=1.[Zn](N=[N+]=[N-])N=[N+]=[N-]>[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:22])([CH3:23])[CH3:21])=[O:18])[CH2:13][C@H:12]1[C@@H:24]([N:27]=[N+:56]=[N-:57])[CH3:25])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 795ImidazoleHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 70212213HCID 70212213, compound

Product 1

HCID 86757593HCID 86757593, compoundYield 51.6%

Reagents, catalysts & solvents 2

HCID 178514646Zinc azideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

(S, R)-1-benzyloxycarbonyl-2-(1-hydroxyethyl)-4-tert-butyloxycarbonyl-piperazine (7.6 g) was dissolved in 208 mL of toluene. While stirring, imidazole (3,5 g), triphenylphospine (15.31 g), and Zn(N3)2.pyr2 (14.11 g) were added in that order. The mixture was cooled to 0° C. and diethylazodicarboxylate (10.2 g) was added dropwise. The mixture was warmed to room temperature and stirred for 1 hour, then decanted into a separatory funnel and extracted with 2×360 mL of ethyl acetate. Any solids in the reaction flask were dissolved with 1N HCl, poured into the separatory funnel, and extracted with 2×760 mL of ethyl acetate. The combined organics were washed with 760 mL each of saturated NaHCO3 and brine, dried with Na2SO4, and concentrated. The residue was purified by flash chromatography, eluting with 4:1 hexanes-ethyl acetate to provide 4.19 g of the title compound. Mass spectrum (ESI) 334.1 (M−55).

Workup

  1. additionpyr2 (14.11 g) were added in that order
  2. temperatureThe mixture was warmed to room temperature
  3. stirringstirred for 1 hour
  4. customdecanted into a separatory funnel
  5. extractionextracted with 2×360 mL of ethyl acetate
  6. dissolutionAny solids in the reaction flask were dissolved with 1N HCl
  7. additionpoured into the separatory funnel
  8. extractionextracted with 2×760 mL of ethyl acetate
  9. washThe combined organics were washed with 760 mL each of saturated NaHCO3 and brine
  10. dry with materialdried with Na2SO4
  11. concentrationconcentrated
  12. customThe residue was purified by flash chromatography
  13. washeluting with 4:1 hexanes-ethyl acetate

Sources & evidence

ORD record
ord-da312566e2454b7ebe00e48e45ab3c07
Source dataset
uspto-grants-2001_11
Patent number
US06316444B1

Reaction notes

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