1,1-Dimethylethyl 15-azido-4,7,10,13-tetraoxapentadecanoate → tert-Butyl 1-amino-3,6,9,12-tetraoxapentadecan-15-oate
Reaction equation
[C:1]([O:5][C:6](=[O:24])[CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][CH2:16][CH2:17][O:18][CH2:19][CH2:20][N:21]=[N+]=[N-])([CH3:4])([CH3:3])[CH3:2]>C(O)C.[Pd]>[C:1]([O:5][C:6](=[O:24])[CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][CH2:16][CH2:17][O:18][CH2:19][CH2:20][NH2:21])([CH3:2])([CH3:4])[CH3:3]Participants
Reactant 1
Product 1
Reagents, catalysts & solvents 2
Procedure
The crude material 18a (3.0 g, 8.0 mmol) was dissolved in ethanol (20 mL) and 300 mg of 10% Pd/C was added. The system was evacuated under vacuum and placed under 1 atm of hydrogen gas via balloon with vigorous stirring, and repeated 4 times to ensure a pure hydrogen atmosphere. The reaction was then stirred overnight at room temperature. TLC showed that the reaction was complete after 16 hrs. The crude reaction was passed through a short pad of celite rinsing with ethyl acetate. The solvent was removed and the amine purified on silica gel using a mixture of 15% methanol and 2.5% triethylamine in methylene chloride as the eluant to give 2.3 g (85% yield) of the desired amine 19a (FIG. 8). 1H NMR: 1.36 (s, 9H), 2.27 (br s., 2H), 2.42 (t, 2H, J=6.4 Hz), 2.80 (t, 2H, J=5.2 Hz), 3.45 (d, 2H, J=5.2 Hz), 3.51-3.59 (m, 12H), 3.63 (d, 2H, J=6.4 Hz). MS: m/z Calculated: 322.21, Found: 321.97.
Workup
- customThe system was evacuated under vacuum
- waitwas complete after 16 hrs
- customThe crude reaction
- washrinsing with ethyl acetate
- customThe solvent was removed
- customthe amine purified on silica gel using
- additiona mixture of 15% methanol and 2.5% triethylamine in methylene chloride as the eluant
Sources & evidence
- ORD record
- ord-85790d7133be4c4a868f1c8953ca9d29
- Source dataset
- uspto-grants-2004_04
- Patent number
- US06716821B2
Reaction notes
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