tert-Butyl [3-({2-[(tert-butoxycarbonyl)amino]-5-nitrophenyl}ethynyl)phenyl]carbamate → Carbamic acid,n-[3-[2-[5-amino-2-[[(1,1-dimethylethoxy)carbonyl]amino]phenyl]ethyl]phenyl]-,1,1-dimethylethyl ester

HRID 541748Notes

Reaction equation

HRID 541748 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-])=O)=[CH:11][C:10]=1[C:18]#[C:19][C:20]1[CH:21]=[C:22]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH:23]=[CH:24][CH:25]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>CN(C=O)C.[Pd]>[NH2:15][C:12]1[CH:13]=[CH:14][C:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])=[C:10]([CH2:18][CH2:19][C:20]2[CH:21]=[C:22]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH:23]=[CH:24][CH:25]=2)[CH:11]=1

Participants

4

Reactant 1

HCID 57962078tert-Butyl [3-({2-[(tert-butoxycarbonyl)amino]-5-nitrophenyl}ethynyl)phenyl]carbamate

Product 1

HCID 57962696Carbamic acid,n-[3-[2-[5-amino-2-[[(1,1-dimethylethoxy)carbonyl]amino]phenyl]ethyl]phenyl]-,1,1-dimethylethyl ester

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of tert-butyl [3-({2-[(tert-butoxycarbonyl)amino]-5-nitrophenyl}ethynyl)phenyl]carbamate (15.0 g, 33.1 mmol) in DMF (234 mL) was added 10% Palladium on carbon (13.1 g, 11.2 mmol). The solution was shaked under 55 psi H2 atmosphere for 72 h. The solution was filtered through a pad of celite. The filtrate was concentrated and purified with silica gel chromatography (45% ethyl acetate/hexanes) to give an intermediate as yellow oil. To a solution of the intermediate in methanol (200 mL) was added 10% Palladium on carbon (12 g). The resulting solution was shaked under 55 psi H2 atmosphere overnight. The reaction mixture was filtered through a pad of celite and the filtrate was concentrated. The crude product was purified with a short pad of silica gel to give the desire product (11.5 g, 81%). LCMS calculated for C24H33N3O4Na (M+Na)+: m/z=450.2.

Workup

  1. filtrationThe solution was filtered through a pad of celite
  2. concentrationThe filtrate was concentrated
  3. custompurified with silica gel chromatography (45% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-3b7929dedd904b4b9fd4eff635e925f7
Source dataset
uspto-grants-2014_10
Patent number
US08871753B2

Reaction notes

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