4-Toluenesulfonyl chloride → (2S,4R)-1-p-nitrobenzyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol p-toluenesulfonate

HRID 1034485Notes

Reaction equation

HRID 1034485 reaction equation
[N+:1]([C:4]1[CH:25]=[CH:24][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@H:15]([O:17][S:18]([CH3:21])(=[O:20])=[O:19])[CH2:14][C@H:13]2[CH2:22][OH:23])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:26]1([CH3:36])[CH:31]=[CH:30][C:29]([S:32](Cl)(=[O:34])=[O:33])=[CH:28][CH:27]=1.C(N(CC)CC)C.CN(C1C=CC=CN=1)C>ClCCl>[C:26]1([CH3:36])[CH:31]=[CH:30][C:29]([S:32]([O:23][CH2:22][C@@H:13]2[CH2:14][C@@H:15]([O:17][S:18]([CH3:21])(=[O:20])=[O:19])[CH2:16][N:12]2[C:10]([O:9][CH2:8][C:7]2[CH:24]=[CH:25][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)=[O:11])(=[O:34])=[O:33])=[CH:28][CH:27]=1

Participants

6

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 218852-DimethylaminopyridineHCID 16093852(2S,trans)-4-Nitrobenzyl 2-(hydroxymethyl)-4-((methylsulfonyl)oxy)pyrrolidine-1-carboxylate

Product 1

HCID 131718416(2S,4R)-1-p-nitrobenzyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol p-toluenesulfonateYield 93%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of (2S,4R)-1-p-nitrobenzyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol (28.8 g: 77 mmole) in dichloromethane (150 ml) under ice cooling, p-toluenesulfonyl chloride (19.11 g: 1.3 eq.), triethylamine (10.4 ml: 1.3 eq.) and dimethylaminopyridine (0.94 g: 0.1 eq.) are added. The mixture is stirred at 25° C. for 7 hours. The reaction mixture is diluted with ice water. The resultant organic layer is taken, successively washed with aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and concentrated in vacuo. The residue is recrystallized from n-hexane to give (2S,4R)-1-p-nitrobenzyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol p-toluenesulfonate (37.7 g). Yield: 93%. NMR δ(CDCl3) ppm: 2.20 to 2.50(m, 1H), 2.44(s, 3H), 3.05(s, 3H), 3.45 to 4.60(m, 5H), 5.18(s, 2H), 5.26(br s, 1H), 7.34(d, J=8 Hz, 2H), 7.50(d, J=8 Hz, 2H), 7.75(d, J=8 Hz, 2H), 8.23(d, J=8 Hz, 2H). IR ν (CHCl3) cm-1 : 1700, 1599.

Workup

  1. washsuccessively washed with aqueous sodium hydrogen carbonate and water
  2. dry with materialdried over magnesium sulfate
  3. concentrationconcentrated in vacuo
  4. customThe residue is recrystallized from n-hexane

Sources & evidence

ORD record
ord-b33ab0b00423448788fae2d95d078183
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

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