Formic Acid → 1,1-Dimethylethyl N-((1S,2S)-3-chloro-2-hydroxy-1-(phenylmethyl)propyl)carbamate
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>ClCCl.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>[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
Reactant 3
Product 1
Reagents, catalysts & solvents 2
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) (1S,2S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine (3.4 mg, 0.005 mmol, s/c=1000) in dichloromethane (10.0 ml), followed by stirring at room temperature for 1 hour. Dichloromethane (20.0 ml) was added to the reaction mixture, and the stirring was continued for 1 hour at room temperature. After completion of the reaction, the reaction mixture was quantitatively analyzed by HPLC to confirm production of a desired compound, (2S, 3S)-3-tert-butoxycarbonylamino-1-chloro-2-hydroxy-4-phenylbutane (1.50 g; yield: 99.9%). The production ratio of the desired (2S,3S)-form to the isomeric (2R,3S)-form, (2S,3S):(2R,3S), was found to be 12.5:1. The resulting dichloromethane solution was evaporated, and the residue was crystallized from a mixed solvent of water, toluene and ethanol (1:1:3) to give a mixture at a (2S,3S) to (2R,3S) ratio of 99.6:0.4 in a yield of 80%.
Workup
- waitthe stirring was continued for 1 hour at room temperature
- customAfter completion of the reaction
Sources & evidence
- ORD record
- ord-767893fd1bdd434c9e3d1d1d09b9c51a
- Source dataset
- uspto-grants-2005_05
- Patent number
- US06888012B2
Reaction notes
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