p-Toluenesulfonic acid monohydrate → (R)-tert-Butyl (1-hydroxybut-3-yn-2-yl)carbamate

HRID 380900Notes

Reaction equation

HRID 380900 reaction equation
[C:1]([N:8]1[C@H:12]([C:13]#[CH:14])[CH2:11][O:10]C1(C)C)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>CO.O>[C:1]([NH:8][C@H:12]([C:13]#[CH:14])[CH2:11][OH:10])([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2]

Participants

5

Reactant 2

HCID 521998p-Toluenesulfonic acid monohydrateHCID 11096274tert-Butyl (4R)-4-ethynyl-2,2-dimethyl-1,3-oxazolidine-3-carboxylate

Product 1

HCID 10921216(R)-tert-Butyl (1-hydroxybut-3-yn-2-yl)carbamate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A solution of (R)-N-Boc-2,2-dimethyl-4-ethynyl-oxazolidine (200 mg, 0.89 mmol) (Example 91A above) in a mixture of MeOH (10 mL) and water (1 mL) was treated with p-toluenesulfonic acid monohydrate (16 mg, 0.09 mmol). After stirring at reflux overnight a thermodynamic mixture of starting material and product was obtained (appr. 1:1). The solvent was concentrated and the product was separated from the starting material via silica gel column chromatography with a 0-60-100% EtOAc in hexanes gradient. The recovered starting material was subjected to the above process for two more times yielding (R)-N-Boc-2-amino-but-3-yn-1-ol. (Yield 150 mg, 91%).

Workup

  1. temperatureat reflux overnight
  2. additiona thermodynamic mixture of starting material
  3. customproduct was obtained (appr. 1:1)
  4. concentrationThe solvent was concentrated
  5. customthe product was separated from the starting material via silica gel column chromatography with a 0-60-100% EtOAc in hexanes gradient

Sources & evidence

ORD record
ord-464c5714e7404ebabf7f5cb0084a4eb2
Source dataset
uspto-grants-2001_10
Patent number
US06303793B1

Reaction notes

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