Triphenylphosphine → HCID 54130044, compound

HRID 840100Notes

Reaction equation

HRID 840100 reaction equation
[O:1]1[CH:13]2[C@@:14]34[CH2:16][CH2:17][N:18]([CH3:19])[C@@H:8]([C@@H:9]3[CH2:10][CH2:11][C:12]2=[O:20])[CH2:7][C:6]2=[C:15]4[C:2]1=[C:3](OS(C(F)(F)F)(=O)=O)[CH:4]=[CH:5]2.[CH:29]([Sn](CCCC)(CCCC)CCCC)=[CH2:30].[Li+].[Cl-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C)C=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH4+:18].[OH-:1].[O:1]1[CH:13]2[C@@:14]34[CH2:16][CH2:17][N:18]([CH3:19])[C@@H:8]([C@@H:9]3[CH2:10][CH2:11][C:12]2=[O:20])[CH2:7][C:6]2=[C:15]4[C:2]1=[C:3]([CH:29]=[CH2:30])[CH:4]=[CH:5]2

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 54452086HCID 54452086, compound

Product 2

HCID 14923Ammonium HydroxideHCID 54130044HCID 54130044, compoundYield 155.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

2 g (4.8 mmol) of 4,5-epoxy-17-methyl-3-trifluoromethanesulfonyloxymorphinan-6-one were dissolved, under a nitrogen atmosphere, in 25 ml of dimethylformamide, then 1.46 ml (5 mmol) of vinyltributyltin, 1.6 g (38.4 mmol) of LiCl, 0.337 g (0.48 mmol) of bis(triphenylphosphine)palladium(II) chloride and 0.5 g (1.9 mmol) of triphenylphosphine were added. The reaction mixture was heated to 100° C. for 3 h, then it was poured onto water and the aqueous phase was extracted with AcOEt. The organic phase was dried over Na2SO4 and the solvent was removed in vacuo. The crude reaction mixture was purified by flash chromatography, eluting with a mixture CH2Cl2/MeOH/conc. NH4OH 90:7:0.7 respectively, yielding 1.1 g of the title product.

Workup

  1. additionit was poured onto water
  2. extractionthe aqueous phase was extracted with AcOEt
  3. dry with materialThe organic phase was dried over Na2SO4
  4. customthe solvent was removed in vacuo
  5. customThe crude reaction mixture
  6. customwas purified by flash chromatography
  7. washeluting with a mixture CH2Cl2/MeOH/conc

Sources & evidence

ORD record
ord-9218c4f7abb64794a2e2fa588c6b145d
Source dataset
uspto-grants-2002_04
Patent number
US06365594B1

Reaction notes

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