Formic Acid → (2S,3S)-3-benzyloxycarbonylamino-1-chloro-2-hydroxy-4-naphthylbutane

HRID 2180340Notes

Reaction equation

HRID 2180340 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20][CH:19]=1)[C:13](=[O:16])[CH2:14][Cl:15])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(O)=O>C(OCC)(=O)C.C1(C)C=CC(S(N[C@@H](C2C=CC=CC=2)[C@H](C2C=CC=CC=2)N)(=O)=O)=CC=1.Cl[Rh+]C1(C)C(C)=C(C)C(C)=C1C>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20][CH:19]=1)[C@H:13]([OH:16])[CH2:14][Cl:15])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 284Formic AcidHCID 86592057(3S)-3-Benzyloxycarbonylamino-1-chloro-4-naphthyl-2-butanone

Product 1

HCID 69803127(2S,3S)-3-benzyloxycarbonylamino-1-chloro-2-hydroxy-4-naphthylbutaneYield 93.3%

Reagents, catalysts & solvents 2

HCID 178425931HCID 178425931, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

(3S)-3-Benzyloxycarbonylamino-1-chloro-4-naphthyl-2-butanone (190.1 mg, 0.5 mmol) and a formic acid/triethylamnine azeotropic mixture (0.1 ml) were added to a solution of chloro(pentamethylcyclopentadienyl)rhodium (III) (1S,2S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine (0.34 mg, 0.0005 mmol, s/c=1000) in ethyl acetate (0.5 ml), followed by stirring at room temperature for 2 hours. After completion of the reaction, purification by silica gel column chromatography gave a desired compound, (2S,3S)-3-benzyloxycarbonylamino-1-chloro-2-hydroxy-4-naphthylbutane (179.0 mg; yield: 93.3%). As a result of HPLC analysis, the production ratio of the desired (2S,3S)-form to the isomeric (2R,3S)-form, (2S,3S):(2R,3S), was 10.9:1. The results of elementary analysis were as follows.

Workup

  1. customAfter completion of the reaction, purification by silica gel column chromatography

Sources & evidence

ORD record
ord-924d0d993cab41ed94b79ef7b6f6f287
Source dataset
uspto-grants-2005_05
Patent number
US06888012B2

Reaction notes

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