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

HRID 618847Notes

Reaction equation

HRID 618847 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 Celite. 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 Celite
  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-87785ac2ec9e4b2ab5e2408fec38a56c
Source dataset
uspto-grants-1999_09
Patent number
US05955610

Reaction notes

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