1,4-Dioxane → (2S,4S)-N-methanesulfonyl-2-tert-butyldimethylsilyloxymethyl-4-diphenylphosphinopyrrolidine

HRID 1638406Notes

Reaction equation

HRID 1638406 reaction equation
O1CCOCC1.Cl[P:8]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[Na].[CH3:22][S:23]([N:26]1[CH2:30][C@H:29](OS(C)(=O)=O)[CH2:28][C@H:27]1[CH2:36][O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])(=[O:25])=[O:24]>O1CCCC1>[CH3:22][S:23]([N:26]1[CH2:30][C@@H:29]([P:8]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH2:28][C@H:27]1[CH2:36][O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:39])[CH3:40])(=[O:24])=[O:25]

Participants

6

Reactant 4

HCID 312751,4-DioxaneHCID 66180ChlorodiphenylphosphineHCID 5360545SodiumHCID 13665135(2S,4R)-N-methanesulfonyl-2-tert-butyldimethylsilyloxymethyl-4-methanesulfonyloxypyrrolidine

Product 1

HCID 13665138(2S,4S)-N-methanesulfonyl-2-tert-butyldimethylsilyloxymethyl-4-diphenylphosphinopyrrolidineYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To 150 ml of dioxane were added 11.39 g (0.052 mol) of chlorodiphenylphosphine and 2.6 g (0.114 mol) of sodium, and the mixture was refluxed for 4 hours in nitrogen atmosphere. After allowing the mixture to stand for cooling, 50 ml of tetrahydrofuran was added to the reaction mixture, and a solution of 10.45 g (0.027 mol) of (2S,4R)-N-methanesulfonyl-2-tert-butyldimethylsilyloxymethyl-4-methanesulfonyloxypyrrolidine [V] in 100 ml of tetrahydrofuran was added dropwise to the mixture lest any air should enter in the reaction system. The mixture was stirred in nitrogen atmosphere at 0° C. for 2 hours and then at room temperature overnight and then any insoluble matter was removed, for example, by filtration. The filtrate was concentrated until dryness under reduced pressure and the residue was purified by column chromatography on silica gel whereby 7.93 g (yield: 62%) of an oily substance was obtained.

Workup

  1. temperaturethe mixture was refluxed for 4 hours in nitrogen atmosphere
  2. temperaturefor cooling
  3. customat room temperature
  4. customovernight
  5. concentrationThe filtrate was concentrated until dryness under reduced pressure
  6. customthe residue was purified by column chromatography on silica gel whereby 7.93 g (yield: 62%) of an oily substance
  7. customwas obtained

Sources & evidence

ORD record
ord-2f511b833e9a47b0bd8bdd3795062de1
Source dataset
uspto-grants-1989_11
Patent number
US04879389

Reaction notes

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