Acetic Acid → 1-(3-O-Acetyl-2,5-dideoxy-beta-L-glycero-pent-4-enofuranosyl)-thymine

HRID 732884Notes

Reaction equation

HRID 732884 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:9]([CH2:10]I)[O:8][C@@H:7]([N:12]2[CH:20]=[C:18]([CH3:19])[C:16](=[O:17])[NH:15][C:13]2=[O:14])[CH2:6]1)(=[O:3])[CH3:2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(O)=O.N(C(OCC)=O)=NC(OCC)=O.C([O-])([O-])=O.[K+].[K+]>C1COCC1.CO>[C:1]([O:4][C@H:5]1[C:9](=[CH2:10])[O:8][C@H:7]([N:12]2[CH:20]=[C:18]([CH3:19])[C:16](=[O:17])[NH:15][C:13]2=[O:14])[CH2:6]1)(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 121116121-(3-O-acetyl-2,5-dideoxy-5-iodo-beta-D-threopentofuranosyl)thymine

Product 1

HCID 670245471-(3-O-Acetyl-2,5-dideoxy-beta-L-glycero-pent-4-enofuranosyl)-thymineYield 127.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 7 (1.08 g, 2.63 mmol), Ph3P (897 mg, 3.42 mmol) and AcOH (301 μL, 5.26 mmol) in THF (10 mL) was cooled to 0 under positive pressure of dry Ar. To this was added dropwise diethyl azodicarboxylate (2.3 M solution in toluene, 1.49 mL, 3.42 mol). After stirring for 30 min, the mixture was partitioned between CH2Cl2 and sat. aqueous NaHCO3. The organic layer was dried (Na2SO4) and evaporated. The residue was treated with K2CO3 (727 mg, 5.26 mmol) in MeOH (5 mL) for 1 h. The mixture was partitioned between CHCl3 and brine. The organic layer was dried (Na2SO4), evaporated, and chromatographed on a silica gel column (hexane/EtOAc=4/1). This gave 8 (892 mg, 83%) as an oil.

Workup

  1. temperaturewas cooled to 0 under positive pressure of dry Ar
  2. customthe mixture was partitioned between CH2Cl2 and sat. aqueous NaHCO3
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. customevaporated
  5. customThe mixture was partitioned between CHCl3 and brine
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. customevaporated
  8. customchromatographed on a silica gel column (hexane/EtOAc=4/1)

Sources & evidence

ORD record
ord-20d7c2d3180c42cd80a80ddeea140622
Source dataset
uspto-grants-2009_09
Patent number
US07589078B2

Reaction notes

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