1,8-Diazabicyclo(5.4.0)undec-7-ene → 5-Azidomethyl-2-(3-methyl-butyryl)-pyridine

HRID 2041477Notes

Reaction equation

HRID 2041477 reaction equation
C1CCN2C(=NCCC2)CC1.O[CH2:13][C:14]1[CH:15]=[CH:16][C:17]([C:20](=[O:25])[CH2:21][CH:22]([CH3:24])[CH3:23])=[N:18][CH:19]=1.C1(P([N:40]=[N+:41]=[N-:42])(C2C=CC=CC=2)=O)C=CC=CC=1>C1(C)C=CC=CC=1.CCOC(C)=O.O>[N:40]([CH2:13][C:14]1[CH:15]=[CH:16][C:17]([C:20](=[O:25])[CH2:21][CH:22]([CH3:24])[CH3:23])=[N:18][CH:19]=1)=[N+:41]=[N-:42]

Participants

7

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 576561925-Hydroxymethyl-2-(3-methyl-butyryl)-pyridine

Product 1

HCID 576563405-Azidomethyl-2-(3-methyl-butyryl)-pyridineYield 106.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Add DBU (240 mg, 1.55 mmol) to a solution of 5-hydroxymethyl-2-(3-methyl-butyryl)-pyridine (250 mg, 1.29 mmol) and diphenylphosphorylazide (430 mg, 1.55 mmol) in anhydrous toluene (10 mL) at 0° C. Stir at 0° C. for 30 min, warm to room temperature and stir for 4 h. Dilute with EtOAc and water. Extract the aqueous phase twice with EtOAc. Dry the combined organic extracts over Na2SO4, filter and concentrate in vacuo. Purify the crude mixture by chromatography on silica gel eluting with hexane and hexane/EtOAc (9:1) to provide the desired intermediate (300 mg, 99%). MS (ES+) m/z: 219 (M+H)+.

Workup

  1. temperaturewarm to room temperature
  2. stirringstir for 4 h
  3. extractionExtract the aqueous phase twice with EtOAc
  4. dry with materialDry the combined organic extracts over Na2SO4
  5. filtrationfilter
  6. concentrationconcentrate in vacuo
  7. customPurify the crude mixture by chromatography on silica gel eluting with hexane and hexane/EtOAc (9:1)

Sources & evidence

ORD record
ord-6bdd62d4007a48cfabba6ab61f82520f
Source dataset
uspto-grants-2013_11
Patent number
US08580780B2

Reaction notes

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