Formic Acid → 1,1-Dimethylethyl N-[(1S,2R)-3-chloro-2-hydroxy-1-(phenylmethyl)propyl]carbamate

HRID 2180332Notes

Reaction equation

HRID 2180332 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:10](=[O:13])[CH2:11][Cl:12])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(O)=O.C(N(CC)CC)C>C(OCC)(=O)C.Cl[Rh+]C1(C)C(C)=C(C)C(C)=C1C.C1(C)C(S(C2C=CC(C(N)C(C3C=CC=CC=3)N)=CC=2)(=O)=O)=CC=CC=1>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[C@@H:10]([OH:13])[CH2:11][Cl:12])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 3

HCID 284Formic AcidHCID 8471TriethylamineHCID 9926241tert-butyl N-((2S)-4-chloro-3-oxo-1-phenylbutan-2-yl)carbamate

Product 1

HCID 99441391,1-Dimethylethyl N-[(1S,2R)-3-chloro-2-hydroxy-1-(phenylmethyl)propyl]carbamateYield 100.1%

Reagents, catalysts & solvents 3

HCID 67043042HCID 67043042, compoundCatalystHCID 178425930HCID 178425930, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

(3S)-3-tert-Butoxycarbonylamino-1-chloro-4-phenyl-2-butanone (1.49 g, 5.0 mmol), 90% formic acid (0.224 ml, 5.25 mmol), and triethylamine (0.730 ml, 5.25 mmol) were added to a solution of chloro(pentamethylcyclopentadienyl)rhodium (III) (1R,2R)-N-(p-toluenesulfonyl-1,2-diphenylethylenediamine (3.4 mg, 0.005 mmol, s/c=1000) in ethyl acetate (7.0 ml), followed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction mixture was quantitatively analyzed by HPLC to confirm production of a desired compound, (2R, 3S)-3-tert-butoxycarbonylamino-1-chloro-2-hydroxy-4phenylbutane (1.50 g; yield: 99.9%). The production ratio of the desired (2R,3S)-form to the isomeric (2S,3S)-form, (2R,3S):(2S,3S), was found to be 9.0:1.

Workup

  1. customAfter completion of the reaction

Sources & evidence

ORD record
ord-38b451d90d444a6bad3223dfa71a9f44
Source dataset
uspto-grants-2005_05
Patent number
US06888012B2

Reaction notes

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