Ethyl Acetate → (2S,4R)-4-methanesulfonyloxy-2-[N-(N,N-dimethylaminomethylene) carbamoyl]-1-(4-nitrobenzyloxycarbonyl) pyrrolidine

HRID 846926Notes

Reaction equation

HRID 846926 reaction equation
[C:1]([C@@H:4]1[CH2:8][C@@H:7]([O:9][S:10]([CH3:13])(=[O:12])=[O:11])[CH2:6][N:5]1[C:14]([O:16][CH2:17][C:18]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=1)=[O:15])(=[O:3])[NH2:2].CO[CH:29](OC)[N:30]([CH3:32])[CH3:31].C(OCC)(=O)C>ClCCl>[CH3:13][S:10]([O:9][C@H:7]1[CH2:6][N:5]([C:14]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=2)=[O:15])[C@H:4]([C:1](=[O:3])[N:2]=[CH:29][N:30]([CH3:32])[CH3:31])[CH2:8]1)(=[O:11])=[O:12]

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 78373Dimethylformamide dimethyl acetalHCID 13455346trans-1-(p-nitrobenzyloxycarbonyl)-4-methanesulfonyloxy-L-prolineamide

Product 1

HCID 57094384(2S,4R)-4-methanesulfonyloxy-2-[N-(N,N-dimethylaminomethylene) carbamoyl]-1-(4-nitrobenzyloxycarbonyl) pyrrolidine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
120 °C

Procedure

To (2S,4R)-2-carbamoyl-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (3 g) was added N,N-dimethylformamide dimethylacetal (3 ml) and the mixture was stirred at 120° C. for 1 hour. The mixture was poured into a mixture of ethyl acetate and dichloromethane, washed with water and brine successively, and evaporated in vacuo to give (2S,4R)-4-methanesulfonyloxy-2-[N-(N,N-dimethylaminomethylene)carbamoyl]-1-(4-nitrobenzyloxycarbonyl)pyrrolidine. The compound obtained above was dissolved in acetic acid (30 ml) and to this solution was added hydrazine hydrate (0.36 ml) at room temperature. After stirring at the same temperature for 2 hours, the mixture was poured into water and ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate and brine successively, dried over magnesium sulfate, and evaporated in vacuo. The oily residue was subjected to a column chromatography on silica gel (90 g) eluting with a mixture of methanol and dichloromethane (1:20 V/V) to give (2S,4R)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)-2-(1H-1,2,4-triazol-3-yl)pyrrolidine (1.5 g).

Workup

  1. washwashed with water and brine successively
  2. customevaporated in vacuo

Sources & evidence

ORD record
ord-444715bd46564a4e880a5472f6d8dd33
Source dataset
uspto-grants-1992_08
Patent number
US05138064

Reaction notes

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