Triphenylphosphine → (R)-N-(tert-butoxycarbonyl)-2-(5-benzyloxy-2-bromophenoxy)-1-(4-benzyloxyphenyl)ethylamine

HRID 460459Notes

Reaction equation

HRID 460459 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.[C:15]([O:19][C:20]([NH:22][C@H:23]([C:26]1[CH:31]=[CH:30][C:29]([O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)=[CH:28][CH:27]=1)[CH2:24][OH:25])=[O:21])([CH3:18])([CH3:17])[CH3:16].[CH2:40]([O:47][C:48]1[CH:49]=[CH:50][C:51]([Br:55])=[C:52](O)[CH:53]=1)[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.O>[C:15]([O:19][C:20]([NH:22][C@H:23]([C:26]1[CH:27]=[CH:28][C:29]([O:32][CH2:33][C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)=[CH:30][CH:31]=1)[CH2:24][O:25][C:50]1[CH:49]=[C:48]([O:47][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[CH:53]=[CH:52][C:51]=1[Br:55])=[O:21])([CH3:18])([CH3:16])[CH3:17]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylate2×HCID 227180755-(Benzyloxy)-2-bromophenolHCID 60086323(R)-2-(tert-butoxycarbonyl)amino-2-(4-benzyloxyphenyl)ethanol

Product 1

HCID 60086347(R)-N-(tert-butoxycarbonyl)-2-(5-benzyloxy-2-bromophenoxy)-1-(4-benzyloxyphenyl)ethylamineYield 75.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Diisopropylazodicarboxylate (0.10 ml, 0.603 mmol) was added to (R)-2-(tert-butoxycarbonyl)amino-2-(4-benzyloxyphenyl)ethanol (161 mg, 0.469 mmol), 5-benzyloxy-2-bromophenol (131 mg, 0.469 mmol) and triphenylphosphine (160 mg, 0.610 mmol) in tetrahydrofuran (3 ml) under a nitrogen stream, followed by stirring for 5 hours at room temperature. Diisopropylazodicarboxylate (0.05 ml, 0.302 mmol) was added to the reaction mixture followed by stirring for 3 hours at room temperature. Water was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/4, v/v) to give (R)-N-(tert-butoxycarbonyl)-2-(5-benzyloxy-2-bromophenoxy)-1(4-benzyloxyphenyl)ethylamine (214 mg, Yield 75%).

Workup

  1. stirringby stirring for 3 hours at room temperature
  2. extractionwas then extracted with ethyl acetate
  3. washThe organic layer was washed sequentially with water and saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/4, v/v)

Sources & evidence

ORD record
ord-1f77e5bbe6bf4ba8b5222d14c2838000
Source dataset
uspto-grants-2007_03
Patent number
US07196081B2

Reaction notes

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