Sodium benzenethiolate → n-Carbobenzoxy-s-phenyl-l-cysteine methyl ester

HRID 1884596Notes

Reaction equation

HRID 1884596 reaction equation
[CH3:1][O:2][C:3](=[O:28])[C@H:4]([CH2:16]O[S:18](C1C=CC(C)=CC=1)(=O)=O)[NH:5][C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7].[CH2:29]([O:36][C:37]([NH:39][C@@H:40]([CH2:45]OS(C)(=O)=O)[C:41]([O:43][CH3:44])=O)=[O:38])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.[CH:51]1[CH:56]=[CH:55][C:54]([S-:57])=[CH:53][CH:52]=1.[Na+]>CN(C=O)C>[CH3:1][O:2][C:3](=[O:28])[C@H:4]([CH2:16][S:57][C:54]1[CH:55]=[CH:56][CH:51]=[CH:52][CH:53]=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].[CH2:29]([O:36][C:37]([NH:39][C@H:40]([CH2:45][C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1)[C:41]([O:43][CH3:44])=[S:18])=[O:38])[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

6

Reactant 3

HCID 4110039Sodium benzenethiolateHCID 7019803Z-Ser(Tos)-OmeHCID 10520504n-Benzyloxycarbonyl-o-mesyl-l-serine methyl ester

Product 2

HCID 10269086n-Carbobenzoxy-s-phenyl-l-cysteine methyl esterHCID 53639929methyl (R)-2-benzyloxycarbonylamino-3-phenylthiopropanoate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Recently, Knight and Sibley (D. W. Knight and A. W. Sibley, J. Chem. Soc., Perkin Trans. 1, 1997, 2179-2187) reported that the displacement of N-benzyloxycarbonyl-O-p-toluenesulfonyl serine methyl ester (or methyl (S)-2-benzyloxycarbonylamino-3-methylsulfonyloxypropanoate) with freshly prepared sodium thiophenylate in DMF at about 0° C. afforded the desired N-benzyloxycarbonyl-S-phenyl-L-cysteine methyl ester (or methyl (R)-2-benzyloxycarbonylamino-3-phenylthiopropanoate) in 98% yield providing a reported optical rotation of [α]20D−17.2 (c, 1.8; MeOH). No enantiomeric ratio of the product was reported. Furthermore, the use of sodium phenolate, prepared from sodium hydride, thiophenol and DMF is not amenable to large scale manufacture.

Sources & evidence

ORD record
ord-dca2b9628e214fb19595ae500ff6dfb5
Source dataset
uspto-grants-2004_07
Patent number
US06765109B1

Reaction notes

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