Dimethyl Sulfate → HCID 89460106, compound

HRID 577729Notes

Reaction equation

HRID 577729 reaction equation
[OH-].[Na+].S(OC)(O[CH3:7])(=O)=O.[C:10]([O:14][C:15]([N:17]1[CH2:21][C@@H:20]([CH2:22][OH:23])[C@H:19]([CH2:24][O:25][Si:26]([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:28])[CH3:27])[CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(Cl)Cl.O>[C:10]([O:14][C:15]([N:17]1[CH2:21][C@@H:20]([CH2:22][O:23][CH3:7])[C@H:19]([CH2:24][O:25][Si:26]([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:27])[CH3:28])[CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11]

Participants

7

Reactant 3

HCID 6497Dimethyl Sulfate2×HCID 14798Sodium HydroxideHCID 59512306HCID 59512306, compound

Product 1

HCID 89460106HCID 89460106, compoundYield 44.2%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Tetrabutylammonium iodide (0.110 g, 0.28 mmol), 50% aqueous NaOH (20 mL) and dimethyl sulfate (0.325 mL, 3.41 mmol) were added to a solution of trans-tert-butyl-3-({[tert-butyl(dimethyl)silyl]oxy}methyl)-4-(hydroxymethyl)pyrrolidine-1-carboxylate (0.982 g, 2.84 mmol) in CH2Cl2 (20 mL). The reaction was stirred at rt overnight. TLC showed some starting material remaining so additional dimethyl sulfate (0.150 mL) was added to the reaction mixture and stirred at rt for 3 hrs. Aqueous NH3OH (30 mL) was added to the reaction mixture and stirred at rt for 1 hr. The mixture was diluted with water (20 mL) and extracted with CH2Cl2 (two×30 mL). The organic layer was dried over MgSO4 and concentrated. The residue was purified via flash chromatography eluting with 10% EtOAc/heptane to give the title compound as a colorless oil (451 mg, 44% yield). 1H NMR (400 MHz, chloroform-d) δ ppm 3.60-3.70 (m, 1H), 3.55 (br. s., 2H), 3.37-3.48 (m, 1H), 3.34 (m, 4H), 3.05-3.23 (m, 2H), 2.22-2.40 (m, 1H), 2.07-2.21 (m, 1H), 1.43-1.49 (m, 9H), 0.89 (s, 9H), 0.05 (s, 6H).

Workup

  1. additionwas added to the reaction mixture
  2. stirringstirred at rt for 3 hrs
  3. additionAqueous NH3OH (30 mL) was added to the reaction mixture
  4. stirringstirred at rt for 1 hr
  5. extractionextracted with CH2Cl2 (two×30 mL)
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated
  8. customThe residue was purified via flash chromatography
  9. washeluting with 10% EtOAc/heptane

Sources & evidence

ORD record
ord-e2f3000bce144c44ab0d4b6fa97dc962
Source dataset
uspto-grants-2015_05
Patent number
US09040547B2

Reaction notes

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