Triethyl phosphite → (+/-)-2-Diethoxyphosphinoyl-5-(p-Toluenesulfonyloxymethyl)-Tetrahydrofuran

HRID 365782Notes

Reaction equation

HRID 365782 reaction equation
C(O[CH:5]1[CH2:9][CH2:8][CH:7]([CH2:10][O:11][S:12]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)(=[O:14])=[O:13])[O:6]1)(=O)C.[P:22]([O:29]CC)([O:26][CH2:27][CH3:28])[O:23][CH2:24][CH3:25].C([O-])(O)=O.[Na+]>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[CH2:24]([O:23][P:22]([O:26][CH2:27][CH3:28])([CH:5]1[CH2:9][CH2:8][CH:7]([CH2:10][O:11][S:12]([C:15]2[CH:16]=[CH:17][C:18]([CH3:21])=[CH:19][CH:20]=2)(=[O:13])=[O:14])[O:6]1)=[O:29])[CH3:25]

Participants

6

Reactant 3

HCID 31215Triethyl phosphiteHCID 516892Sodium BicarbonateHCID 21255879(+/-)-2-Acetoxy-5-(p-Toluenesulfonyloxymethyl)-Tetrahydrofuran

Product 1

HCID 21255867(+/-)-2-Diethoxyphosphinoyl-5-(p-Toluenesulfonyloxymethyl)-Tetrahydrofuran

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
-35 °C

Procedure

To a stirring solution of (±)-2-acetoxy-5-(p-toluenesulfonoxymethyl)-tetrahydrofuran (example 59) (1.63 g, 5.19 mmol) and triethyl phosphite (1.16 mL, 6.75 mmol) in methylene chloride (75 mL) at -35° C. was added titanium (IV) chloride (0.57 mL, 5.19 mmol) dropwise. The yellow solution was then stirred at -35° C. for 30 min and then at 0° C. for 30 min. Saturated NaHCO3 (75 mL) was then added to the reaction mixture and the suspension was then filtered through a CELITE diatomaceous earth. The mixture was then partitioned followed by extraction of the aqueous phase with methylene chloride (2×50 mL). The combined extracts were then washed with brine (100 mL), dried (MgSO4) and concentrated. The residue was then purified by chromatography eluting with 75% EtAc/hexanes→EtAc giving the title compound as 1:1 mixture of cis and trans isomers (1.42 g, 78%).

Workup

  1. waitat 0° C. for 30 min
  2. filtrationthe suspension was then filtered through a CELITE diatomaceous earth
  3. customThe mixture was then partitioned
  4. extractionfollowed by extraction of the aqueous phase with methylene chloride (2×50 mL)
  5. washThe combined extracts were then washed with brine (100 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customThe residue was then purified by chromatography
  9. washeluting with 75% EtAc/hexanes→EtAc

Sources & evidence

ORD record
ord-b0bbcd7f2f0448e883415f917715ab11
Source dataset
uspto-grants-2000_10
Patent number
US06127540

Reaction notes

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