Triphenylphosphine → HCID 57304653, compound

HRID 975671Notes

Reaction equation

HRID 975671 reaction equation
[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@H:10](O)[CH2:9][C@H:8]1[CH2:13][C:14]1[CH:15]=[N:16][N:17]([CH3:19])[CH:18]=1)=[O:6])[CH:2]=[CH2:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[C:51]([OH:59])(=[S:58])[C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1>O1CCCC1>[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@@H:10]([S:58][C:51](=[O:59])[C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[CH2:9][C@H:8]1[CH2:13][C:14]1[CH:15]=[N:16][N:17]([CH3:19])[CH:18]=1)=[O:6])[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 53841431HCID 53841431, compoundHCID 178526132HCID 178526132, compound

Product 1

HCID 57304653HCID 57304653, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2R,4R)-1-allyloxycarbonyl-4-hydroxy-2-{(1-methylpyrazol-4-yl)methyl)pyrrolidine (15.3 g) and triphenylphosphine (19.67 g) in tetrahydrofuran (180 ml) was added diethyl azodicarboxylate (13.06 g) at -30° C. After 15 minutes, thiobenzoic acid (9.5 ml) was added thereto. The mixture was warmed up to 0°~5° C. over 25 minutes and stirred for 2 hours. After evaporation of tetrahydrofuran, the resulting residue was dissolved in ethyl acetate (500 ml). The organic layer was washed with saturated sodium bicarbonate solution (×3), water and brine, dried over magnesium sulfate and evaporated under reduced pressure. After storing the residue overnight in an ice box, a precipitate had appeared. To the precipitate was added a solution of diisopropyl ether (IPE)--diethyl ether (1:1, 100 ml) and the solid was removed by filtration. The filtrate was evaporated and the residue was column chromatographed on silica gel (1.1 kg, eluting with AcOEt-IPE=2:3 to 1:1) to give (2R,4S)-1-allyloxycarbonyl-4-benzoylthio-2-{(1-methylpyrazol-4-yl)methyl}pyrrolidine (21.8 g).

Workup

  1. temperatureThe mixture was warmed up to 0°~5° C. over 25 minutes
  2. customAfter evaporation of tetrahydrofuran
  3. dissolutionthe resulting residue was dissolved in ethyl acetate (500 ml)
  4. washThe organic layer was washed with saturated sodium bicarbonate solution (×3), water and brine
  5. dry with materialdried over magnesium sulfate
  6. customevaporated under reduced pressure
  7. customthe residue overnight
  8. additionTo the precipitate was added a solution of diisopropyl ether (IPE)
  9. customdiethyl ether (1:1, 100 ml) and the solid was removed by filtration
  10. customThe filtrate was evaporated
  11. customchromatographed on silica gel (1.1 kg, eluting with AcOEt-IPE=2:3 to 1:1)

Sources & evidence

ORD record
ord-e078b6fadfff4206b7fb6f4ed00b5ee3
Source dataset
uspto-grants-1997_03
Patent number
US05608056

Reaction notes

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