Triphenylphosphine → HCID 87593598, compound

HRID 626650Notes

Reaction equation

HRID 626650 reaction equation
[Si:1]([O:8][C@H:9]1[CH2:13][C@@H:12](O)[C:11](=[CH2:15])[C@@H:10]1[CH2:16][O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Cl:25][C:26]1[N:34]=[C:33]([NH2:35])[N:32]=[C:31]2[C:27]=1[NH:28][CH:29]=[N:30]2.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1>[Si:1]([O:8][C@H:9]1[CH2:13][C@H:12]([N:30]2[CH:29]=[N:28][C:27]3[C:31]2=[N:32][C:33]([NH2:35])=[N:34][C:26]=3[Cl:25])[C:11](=[CH2:15])[C@@H:10]1[CH2:16][O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:19])[CH3:20])([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 53603492-Amino-6-chloropurine2×HCID 5462977Diethyl azodicarboxylateHCID 56651232(1R,3R,4S)-4-{[tert-Butyl(dimethyl)silyl]oxy}-3-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2-methylidenecyclopentan-1-ol2×

Product 1

HCID 87593598HCID 87593598, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-23 °C

Procedure

370 mg (1.0 mmol) (1R,3R,4S)-4-(tert-butyldimethylsilyloxy)-3-[(tert-butyldimethylsilyloxy)methyl]-2-methylene-cyclopentanol (Compound 4a, R1═R2=t-BuMe2Si), 338 mg (2.0 mmol) 6-chloro-2-aminopurine (Compound 23) and 524 mg Ph3P (2.0 mmol) were placed into 20 ml round bottom flask, to which 5 ml anhydrous THF was then added. The mixture was cooled to −23° C., to which a solution of 350 mg DEAD (1.0 mmol)/5 ml THF was added dropwise. After addition was completed, the reaction mixture was stirred at −23° C. for 3.5 hours, warmed to room temperature and stirred at room temperature overnight. Subsequently THF was evaporated off under reduced pressure. 10 ml t-BuOMe was added to the residue. The mixture was stirred for 5 minutes, to which 15 ml n-hexane was added. The mixture was maintained standing for 5 hours, and filtered to remove insoluble substance. The filtrate was purified with column chromatography, eluting with petroleum ether/EtOAc (3/1 (v/v)), to afford 305 mg (59%) of title compound as light yellow oil.

Workup

  1. additionwas then added
  2. additionwas added dropwise
  3. additionAfter addition
  4. temperaturewarmed to room temperature
  5. stirringstirred at room temperature overnight
  6. customSubsequently THF was evaporated off under reduced pressure
  7. addition10 ml t-BuOMe was added to the residue
  8. stirringThe mixture was stirred for 5 minutes, to which 15 ml n-hexane
  9. additionwas added
  10. temperatureThe mixture was maintained
  11. waitstanding for 5 hours
  12. filtrationfiltered
  13. customto remove insoluble substance
  14. customThe filtrate was purified with column chromatography
  15. washeluting with petroleum ether/EtOAc (3/1 (v/v))

Sources & evidence

ORD record
ord-c08e290bd2974c33ab6c8778e3b4e32c
Source dataset
uspto-grants-2016_04
Patent number
US09309249B2

Reaction notes

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