N-(benzyloxycarbonyl)-4-[[(1,1-dimethylethoxy)carbonyl]amino]-3-methyl-dehydrophenylalanine methyl ester → N-(benzyloxycarbonyl)-4-[(1,1-dimethylethoxy)carbonyl]amino-3-methyl-L-phenylalanine methyl ester

HRID 844872Notes

Reaction equation

HRID 844872 reaction equation
[CH3:1][O:2][C:3](=[O:32])[C:4](=[CH:16][C:17]1[CH:22]=[CH:21][C:20]([NH:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])=[C:19]([CH3:31])[CH:18]=1)[NH:5][C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7]>CO>[CH3:1][O:2][C:3](=[O:32])[C@H:4]([CH2:16][C:17]1[CH:22]=[CH:21][C:20]([NH:23][C:24]([O:26][C:27]([CH3:28])([CH3:29])[CH3:30])=[O:25])=[C:19]([CH3:31])[CH:18]=1)[NH:5][C:6]([O:8][CH2:9][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)=[O:7]

Participants

3

Reactant 1

HCID 69848286N-(benzyloxycarbonyl)-4-[[(1,1-dimethylethoxy)carbonyl]amino]-3-methyl-dehydrophenylalanine methyl ester

Product 1

HCID 69336452N-(benzyloxycarbonyl)-4-[(1,1-dimethylethoxy)carbonyl]amino-3-methyl-L-phenylalanine methyl esterYield 55.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A stream of argon was passed through a solution of N-(benzyloxycarbonyl)-4-[[(1,1-dimethylethoxy)carbonyl]amino]-3-methyl-dehydrophenylalanine methyl ester (8.08 mmol, 3.56 g) in methanol (25 mL) in a Parr pressure vessel overnight. Then, the catalyst, (+)-1,2-bis((2S,5S)-2,5-dimethylphospholano)benzene(cyclooctadiene)rhodium (I) trifluoromethanesulfonate [[Rh(COD)(S,S)-(me)DuPHOS]+TfO-] (˜40 mg) was added under a stream of argon in a glove box. The solution was stirred under a hydrogen pressure (60 psi) at room temperature for 22 h. The resulting solution was concentrated and the crude product was purified by silica gel chromatography using a Biotage (40m) column to obtain 2 g (55% yield) of N-(benzyloxycarbonyl)-4-[[(1,1-dimethylethoxy)carbonyl]amino]-3-methyl-L-phenylalanine methyl ester as an amorphous white solid. EI-HRMS m/e calcd for C24H30N2O6 (M+) 442.1627, found 442.1629.

Workup

  1. concentrationThe resulting solution was concentrated
  2. customthe crude product was purified by silica gel chromatography

Sources & evidence

ORD record
ord-0705799659f34ae983203f7cb7c21aca
Source dataset
uspto-grants-2002_04
Patent number
US06380387B1

Reaction notes

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