Triphenylphosphine → HCID 18647640, compound

HRID 128568Notes

Reaction equation

HRID 128568 reaction equation
[Cl:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[NH:4][CH:5]=[N:6]2.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[O:42]([C@:50]([C@@H:58]([CH:60]([O:62][Si:63]([C:66]([CH3:69])([CH3:68])[CH3:67])([CH3:65])[CH3:64])[OH:61])[OH:59])([OH:57])[C:51]([F:56])([F:55])[C:52](O)=[O:53])[Si:43]([C:46]([CH3:49])([CH3:48])[CH3:47])([CH3:45])[CH3:44]>O1CCCC1>[Cl:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[C:52]([C:51]([F:56])([F:55])[C@@:50]([O:42][Si:43]([C:46]([CH3:49])([CH3:48])[CH3:47])([CH3:45])[CH3:44])([C@@H:58]([CH:60]([O:62][Si:63]([C:66]([CH3:69])([CH3:68])[CH3:67])([CH3:65])[CH3:64])[OH:61])[OH:59])[OH:57])=[O:53]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 53592776-ChloropurineHCID 18647641HCID 18647641, compound2×

Product 1

HCID 18647640HCID 18647640, compoundYield 34.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 0.77 g (5.0 mmol) of 6-chloro-purine in 50 ml of tetrahydrofuran was added 1.31 g (5.0 mmol) of triphenylphosphine and 0.87 g (5.0 mmol) of diethyl azodicarboxylate. To this solution was added a solution of 1.99 g (5.0 mmol) of 3,5-bis(t-butyldimethylsiloxy)-1-hydroxy-2-desoxy-2,2-difluororibose in tetrahydrofuran. The reaction mixture was stirred at room temperature for approximately 60 hours and an additional 0.66 g (1.7 mmol) of 3,5-bis(t-butyldimethylsiloxy)-1-hydroxy-2-desoxy-2,2-difluororibose was added to the reaction mixture. The mixture was stirred for an additional 6 hours at room temperature. The solvent was evaporated under vacuum and the residue was stirred in a small amount of diethyl ether overnight. The precipitated solid was removed by vacuum filtration and the filtrate was concentrated under vacuum to dryness. The residue was chromatographed over 70 g of silica and eluted with chloroform. Fractions containing the major component were combined and the solvent was evaporated therefrom to provide 1.0 g of 1-(6-chloro-9H-purin-9-yl)-3,5-bis(t-butyldimethylsiloxy)-2-desoxy-2,2-difluororibose. The structure of the product was verified by NMR. Mass spec.=477 [534-(t-butyl)]

Workup

  1. stirringThe mixture was stirred for an additional 6 hours at room temperature
  2. customThe solvent was evaporated under vacuum
  3. stirringthe residue was stirred in a small amount of diethyl ether overnight
  4. customThe precipitated solid was removed by vacuum filtration
  5. concentrationthe filtrate was concentrated under vacuum to dryness
  6. customThe residue was chromatographed over 70 g of silica
  7. washeluted with chloroform
  8. additionFractions containing the major component
  9. customthe solvent was evaporated

Sources & evidence

ORD record
ord-94b21aa955704817ac98171ce64cec69
Source dataset
uspto-grants-1995_11
Patent number
US05464826

Reaction notes

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