Hydrochloric Acid → (2S,4S)-N-methanesulfonyl-4-diphenylphosphinyl-2-hydroxymethylpyrrolidine

HRID 1638407Notes

Reaction equation

HRID 1638407 reaction equation
[CH3:1][S:2]([N:5]1[CH2:9][C@@H:8]([P:10]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:7][C@H:6]1[CH2:23][O:24][Si](C(C)(C)C)(C)C)(=[O:4])=[O:3].[OH:32]O.Cl.O>CO>[CH3:1][S:2]([N:5]1[CH2:9][C@@H:8]([P:10]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:32])[CH2:7][C@H:6]1[CH2:23][OH:24])(=[O:4])=[O:3]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 962WaterHCID 13665138(2S,4S)-N-methanesulfonyl-2-tert-butyldimethylsilyloxymethyl-4-diphenylphosphinopyrrolidine

Product 1

HCID 13665140(2S,4S)-N-methanesulfonyl-4-diphenylphosphinyl-2-hydroxymethylpyrrolidine

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Conditions

Temperature
0 °C

Procedure

In 180 ml of methanol was dissolved 8.39 g (0.0176 mol) of 2S,4S)-N-methanesulfonyl-2 -tert-butyldimethlysilyloxymethyl-4-di-phosphinopyrrolidine [VI], and 11.85 g (0.0348 mol) of 10% hydrogen peroxide was added dropwise to the solution under ice-cooling. The mixture was stirred at 0° C. for one hour and then at room temperature for one hour. To the mixture was then slowly added dropwise a liquid mixture of 8.6 g of 35% hydrochloric acid, 52.7 g of water and 38.7 g of methanol, and the mixture was stirred for 2 hours at room temperature. Any insoluble matter was removed from the mixture by filtration and the filtrate was concentrated under reduced pressure. The concentrate was dissolved in 50 ml of water and the aqueous solution was extracted three times with 100 ml of methylene chloride in each case. The extract was washed with a saturated solution of sodium hydrogen carbonate, dried over magnesium sulfate and concentrated under reduced pressure whereby white crystals were obtained which were then recrystallized from a mixture of ethanol and isopropyl alcohol. Yield 5.3 g (80%), melting point: 138°-139° C.

Workup

  1. additionwas added dropwise to the solution under ice-
  2. temperaturecooling
  3. waitat room temperature for one hour
  4. additionTo the mixture was then slowly added dropwise
  5. stirringthe mixture was stirred for 2 hours at room temperature
  6. customAny insoluble matter was removed from the mixture by filtration
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. dissolutionThe concentrate was dissolved in 50 ml of water
  9. extractionthe aqueous solution was extracted three times with 100 ml of methylene chloride in each case
  10. washThe extract was washed with a saturated solution of sodium hydrogen carbonate
  11. dry with materialdried over magnesium sulfate
  12. concentrationconcentrated under reduced pressure whereby white crystals
  13. customwere obtained which
  14. customwere then recrystallized from a mixture of ethanol and isopropyl alcohol

Sources & evidence

ORD record
ord-1a491f84139942828f2876bfec5f6dde
Source dataset
uspto-grants-1989_11
Patent number
US04879389

Reaction notes

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