Ammonium Chloride → HCID 121396363, compound

HRID 60697Notes

Reaction equation

HRID 60697 reaction equation
[CH3:1][Mg]Br.[CH3:4][C:5]1([CH3:16])[O:9][C@H:8]2[O:10][C@H:11]([C@H:13]3[CH2:15][O:14]3)[CH2:12][C@H:7]2[O:6]1.[NH4+].[Cl-]>C1COCC1.[Cu]I>[CH3:4][C:5]1([CH3:16])[O:9][C@H:8]2[O:10][C@H:11]([C@H:13]([OH:14])[CH2:15][CH3:1])[CH2:12][C@H:7]2[O:6]1

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 10910249(3aR,5S,6aR)-2,2-dimethyl-5-[(2R)-oxiran-2-yl]-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole2×HCID 178418573HCID 178418573, compound

Product 1

HCID 121396363HCID 121396363, compoundYield 75.5%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of CuI (19.3 g, 107 mmol) in dry THF (2000 mL) under N2 atmosphere was added methyl magnesium bromide (3 M in diethyl ether, 537 mL, 1.61 mol) at −70° C. After being stirred at this temperature for 1 hour, a solution of (3aR,5S,6aR)-2,2-dimethyl-5-[(2R)-oxiran-2-yl]-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole (compound 6b, 100 g, 537 mmol, dissolved in anhydrous THF 200 mL) was added to reaction mixture dropwise. After being stirred at −70° C. for additional 2 hours, the reaction mixture was poured into saturated NH4Cl solution. The organic layer was separated and the aqueous phase was extracted with EtOAc twice. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 1:3 EtOAc in petroleum ether) to afford 82 g of (1R)-1-[(3aR,5S,6aR)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]propan-1-ol (compound 6c) as a slight yellow solid.

Workup

  1. stirringAfter being stirred at −70° C. for additional 2 hours
  2. customThe organic layer was separated
  3. extractionthe aqueous phase was extracted with EtOAc twice
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by column chromatography on silica gel (eluting with 1:3 EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-e0ce30c523b2417cade7f8e5c4933e00
Source dataset
uspto-grants-2016_09
Patent number
US09441008B2

Reaction notes

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