Acetic acid, 2-(triphenylphosphoranylidene)-, methyl ester → HCID 67150729, compound

HRID 2220863Notes

Reaction equation

HRID 2220863 reaction equation
[CH2:1]([NH:3][C:4]([NH:6][C:7]1[N:15]=[CH:14][N:13]=[C:12]2[C:8]=1[N:9]=[CH:10][N:11]2[CH:16]1[CH:23]2[CH:19]([O:20][CH:21]([CH:24]=[CH:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)[O:22]2)[CH:18]([CH2:32]O)[O:17]1)=[O:5])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[CH3:56][O:57][C:58]([CH:60]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:59]>C(#N)C.C(OCC)(=O)C>[CH3:56][O:57][C:58](=[O:59])[CH:60]=[CH:32][CH:18]1[CH:19]2[CH:23]([O:22][CH:21]([CH:24]=[CH:25][C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[O:20]2)[CH:16]([N:11]2[CH:10]=[N:9][C:8]3[C:12]2=[N:13][CH:14]=[N:15][C:7]=3[NH:6][C:4]([NH:3][CH2:1][CH3:2])=[O:5])[O:17]1

Participants

6

Reactant 3

HCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterHCID 159087TriacetoxyperiodinaneHCID 67150809HCID 67150809, compound

Product 1

HCID 67150729HCID 67150729, compoundYield 71%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

1-Ethyl-3-[9-(6-hydroxymethyl-2-styryl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yl)-9H-purin-6-yl]-urea (5.0 g, 11 mmol) was suspended in dry acetonitrile (50 mL) and Dess-Martin periodinate (6.7 g, 16 mmol) was added. The suspension was stirred 2 h, after which time proton NMR of an aliquot showed complete conversion to the aldehyde. (Methoxycarbonylmethylene)triphenylphosphorane (3.9 g, 12 mmol) was added and stirring was continued overnight. The reaction mixture was then diluted with ethyl acetate (300 mL), washed with saturated sodium bicarbonate/thiosulfate solution (100 mL), dried with sodium sulfate and filtered. The filtrate was evaporated and the solid was dissolved in hot isopropyl alcohol (50 mL). It was allowed to cool, then heptane was added and it was stirred overnight. The resulting precipitate was washed with heptane and dried under vacuum, affording the desired product (2.9 g, 71%). 1H-NMR (300 MHz, d6DMSO) δ1.15 (t, 3H, J=7 Hz), 3.21 (q, 2H, J=7 Hz), 3.59 (s, 3H), 4.98 (m, 1H), 5.28 (ψt, 1H, J=6 Hz), 5.51 (dd, 1H, J=6 Hz, <2 Hz), 5.70 (d, 1H, J=16 Hz), 5.90 (d, 1H, J=6 Hz), 6.30 (dd, 1H, J=6 Hz, 16 Hz), 6.45 (d, 1H, J<2 Hz), 6.95 (d, 1H, J=15 Hz), 7.35 (m, 3H), 7.45 (d, 2H, J=7 Hz), 8.50 (s, 1H), 8.60 (s, 1H), 9.30 (t, 1H, J=6 Hz), 9.60 (s, 1H).

Workup

  1. stirringstirring
  2. waitwas continued overnight
  3. washwashed with saturated sodium bicarbonate/thiosulfate solution (100 mL)
  4. dry with materialdried with sodium sulfate
  5. filtrationfiltered
  6. customThe filtrate was evaporated
  7. dissolutionthe solid was dissolved in hot isopropyl alcohol (50 mL)
  8. temperatureto cool
  9. additionheptane was added
  10. stirringit was stirred overnight
  11. washThe resulting precipitate was washed with heptane
  12. customdried under vacuum

Sources & evidence

ORD record
ord-7c0dca714ade4ed3ae2b1c57f3e2d114
Source dataset
uspto-grants-2008_05
Patent number
US07368438B2

Reaction notes

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