Hydrochloric Acid → (2S,trans)-4-Nitrobenzyl 2-(hydroxymethyl)-4-((methylsulfonyl)oxy)pyrrolidine-1-carboxylate

HRID 1034484Notes

Reaction equation

HRID 1034484 reaction equation
C[O:2][C:3]([C@@H:5]1[CH2:9][C@@H:8]([O:10][S:11]([CH3:14])(=[O:13])=[O:12])[CH2:7][N:6]1[C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=1)=[O:16])=O.[BH4-].[Na+].Cl>C(O)C.O1CCCC1.O>[N+:25]([C:22]1[CH:23]=[CH:24][C:19]([CH2:18][O:17][C:15]([N:6]2[CH2:7][C@H:8]([O:10][S:11]([CH3:14])(=[O:13])=[O:12])[CH2:9][C@H:5]2[CH2:3][OH:2])=[O:16])=[CH:20][CH:21]=1)([O-:27])=[O:26]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 57030081(2S,4R)-2-Methyl 1-(4-nitrobenzyl) 4-((methylsulfonyl)oxy)pyrrolidine-1,2-dicarboxylate

Product 1

HCID 16093852(2S,trans)-4-Nitrobenzyl 2-(hydroxymethyl)-4-((methylsulfonyl)oxy)pyrrolidine-1-carboxylateYield 70,372.703%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (2S,4R)-1-p-nitrobenzyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-carboxylic acid methyl ester (79.4 g: 0.197 mmole) in a mixture of ethanol (300 ml) and tetrahydrofuran (150 ml), sodium borohydride (10.44 g: 1.4 eq.) is added in small portions with stirring at 0° C. The mixture is stirred at 0° C. for 1.5 hours and at room temperature for 5 hours. To the reaction mixture under ice cooling, 5N-hydrochloric acid (100 ml) is added. The mixture is diluted with water, and extracted with ethyl acetate. The extract is washed with brine, dried over sodium sulfate, and concentrated in vacuo. The residue is recrystallized from a mixture of dichloromethane and ether to give (2S,4R)-1-p-nitrobenzyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol (51.9 g). Yield: 70%. NMR δ(CDCl3) ppm: 1.93 to 2.14(m, 1H), 2.32 to 2.48(m, 1H), 3.06(s, 3H), 3.53 to 4.28(m, 6H), 5.26(s, 2H), 7.53(d, J=9 Hz, 2H), 8.24(d, J=9 Hz, 2H). IR ν (CHCl3) cm-1 : 3404, 1698, 1607.

Workup

  1. additionis added in small portions
  2. stirringThe mixture is stirred at 0° C. for 1.5 hours and at room temperature for 5 hours
  3. extractionextracted with ethyl acetate
  4. washThe extract is washed with brine
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue is recrystallized from a mixture of dichloromethane and ether

Sources & evidence

ORD record
ord-0c949561a72a4053a61b1e6b166f91d7
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

Loading…