Carbon tetrabromide → 2-Azidomethyl-6-[(tert-butyldimethylsilyloxy)methyl]pyridine
Reaction equation
[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH2:16]O)[N:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[N-:18]=[N+:19]=[N-:20].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)Br>>[N:18]([CH2:16][C:12]1[CH:13]=[CH:14][CH:15]=[C:10]([CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[N:11]=1)=[N+:19]=[N-:20]Participants
Procedure
A mixture of 2-[(tert-butyldimethylsilyloxy)methyl]-6-hydroxymethylpyridine (1) (2.14 g, 8.42 mmol), sodium azide (2.73 g, 42.0 mmol), triphenylphosphine (2.65 g, 10.10 mmol), and carbon tetrabromide (3.07 g, 9.29 mmol) was dried in vacuo, and dissolved in DMF (64 mL). To the solution was added triethylamine (2.64 mL) and stirred for 25 hours under Ar atmosphere. TLC was used to confirm there was no starting material in the reaction mixture. Then, the mixture was subjected to extraction with EtOAc and water. The organic layer was washed with sat. NaCl aq., dried over anhydrous Na2SO4, and evaporated under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography (Hex:EtOAc=50:1) to give 2-azidomethyl-6-[(tert-butyldimethylsilyloxy)methyl]pyridine (2) (1.77 g, 76%) as a pale-yellow oil.
Workup
- customwas dried in vacuo
- dissolutiondissolved in DMF (64 mL)
- additionTo the solution was added triethylamine (2.64 mL)
- extractionThen, the mixture was subjected to extraction with EtOAc and water
- washThe organic layer was washed with sat. NaCl aq.
- dry with materialdried over anhydrous Na2SO4
- customevaporated under reduced pressure
- customto remove the solvent
- customThe residue was purified by silica gel column chromatography (Hex:EtOAc=50:1)
Sources & evidence
- ORD record
- ord-c3c7f100fd614dd4a9d91eb2e25a4ab8
- Source dataset
- uspto-grants-2014_01
- Patent number
- US08633304B2
Reaction notes
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