Z-Leu-chloromethylketone → (2R, 3S)-3-benzyloxycarbonylamino-1-chloro-2-hydroxy-5-methylhexane

HRID 2180336Notes

Reaction equation

HRID 2180336 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][CH:18]([CH3:20])[CH3:19])[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(N(CC)CC)C>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][CH:18]([CH3:20])[CH3:19])[C@@H:13]([OH:16])[CH2:14][Cl:15])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 7020262Z-Leu-chloromethylketoneHCID 11084032Triethylammonium formate

Product 1

HCID 21729192(2R, 3S)-3-benzyloxycarbonylamino-1-chloro-2-hydroxy-5-methylhexaneYield 98.6%

Reagents, catalysts & solvents 2

HCID 178425932HCID 178425932, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

(3S)-3-Benzyloxycarbonylamino-1-chloro-5-methyl-2-hexanone (298.7 mg, 1.0 mmol) and a formic acid/triethylamine azeotropic mixture (0.2 ml) were added to a solution of chloro(pentamethylcyclopentadienyl)rhodium (III) (1R,2R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine (0.67 mg, 0.001 mmol, s/c=1000) in ethyl acetate (1.0 ml), followed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction mixture was purified by silica gel column chromatography to give a desired compound, (2R, 3S)-3-benzyloxycarbonylamino-1-chloro-2-hydroxy-5-methylhexane (295.6 mg; yield: 98.5%). HPLC analysis revealed that the production ratio of the desired (2R,3S)-form to the isomeric (2S,3S)-form, (2R,3S):(2S,3S), was 4.9:1. The results of elementary analysis were as follows.

Workup

  1. customAfter completion of the reaction
  2. customthe reaction mixture was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-dbc6378cf7304a0cbba128c76386c695
Source dataset
uspto-grants-2005_05
Patent number
US06888012B2

Reaction notes

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