Sulfuric Acid → (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol

HRID 1034528Notes

Reaction equation

HRID 1034528 reaction equation
[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[CH2:9][C@H:8]1[C:17](OC)=[O:18])=[O:6])[CH:2]=[CH2:3].[BH4-].[Na+].S(=O)(=O)(O)O>O1CCCC1.C(O)C>[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@H:10]([O:12][S:13]([CH3:16])(=[O:14])=[O:15])[CH2:9][C@H:8]1[CH2:17][OH:18])=[O:6])[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 4311764Sodium borohydrideHCID 10733517(2S,4R)-N-allyloxycarbonyl-4-methanesulfonyloxyproline methyl ester

Product 1

HCID 18639172(2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanolYield 93.5%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxy-2-methoxycarbonylpyrrolidine (27.12 g: 74.0 mmole) in a mixture of tetrahydrofuran (94 ml) and ethanol (140 ml), sodium borohydride (12 g: 31.7 mmole) is added in a nitrogen atmosphere under ice cooling. The mixture is stirred for 4 hours at room temperature. To the reaction mixture concentrated sulfuric acid (8.8 ml: 158.4 mmole) is added dropwise under ice cooling. The reaction mixture is concentrated to half a volume in vacuo, and diluted with ethyl acetate (100 ml) and ice water (100 ml). The organic layer is taken, successively washed with aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate, and concentrated in vacuo to give (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol (19.33 g). Yield: 77%. Colorless oil. NMR δ(CDCl3) ppm: 1.9 to 2.1(m, 1H), 2.3 to 2.5(m, 1H), 3.05(s, 3H), 3.5 to 3.7(m, 2H), 3.7 to 4.1(m, 2H), 4.1 to 4.3(m, 1H), 4.6(m, 2H), 5.2 to 5.4(m, 3H), 5.8 to 6.1(m, 1H).

Workup

  1. additionis added in a nitrogen atmosphere under ice cooling
  2. concentrationThe reaction mixture is concentrated to half a volume in vacuo
  3. additiondiluted with ethyl acetate (100 ml) and ice water (100 ml)
  4. washsuccessively washed with aqueous sodium hydrogen carbonate and saturated brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ff0cdf2580e84edc99121273787baf22
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

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