Azobisisobutyronitrile → 1-[(2S,4R,5R)-4-allyl-5-(5-amino-2,7-dioxo-6H-thiazolo[4,5-d]pyrimidin-3-yl)tetrahydrofuran-2-yl]propyl benzoate

HRID 60734

Reaktionsgleichung

Reaktionsgleichung von HRID 60734
[C:1]([O:9][CH:10]([C@@H:13]1[CH2:17][C@@H:16](OC(OC2C=CC=CC=2)=S)[C@H:15]([N:28]2[C:32]3[N:33]=[C:34]([NH2:38])[NH:35][C:36](=[O:37])[C:31]=3[S:30][C:29]2=[O:39])[O:14]1)[CH2:11][CH3:12])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N(C(C)(C)C#N)=N[C:42](C)([CH3:45])[C:43]#N.C([Sn](CCCC)(CCCC)CCCC)C=C>C1(C)C=CC=CC=1>[C:1]([O:9][CH:10]([C@@H:13]1[CH2:17][C@@H:16]([CH2:45][CH:42]=[CH2:43])[C@H:15]([N:28]2[C:32]3[N:33]=[C:34]([NH2:38])[NH:35][C:36](=[O:37])[C:31]=3[S:30][C:29]2=[O:39])[O:14]1)[CH2:11][CH3:12])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

5

Edukt 3

HCID 6547AzobisisobutyronitrileHCID 90628AllyltributylstannaneHCID 1371087421-[(2S,4R,5R)-5-(5-amino-2,7-dioxo-6H-thiazolo[4,5-d]pyrimidin-3-yl)-4-phenoxycarbothioyloxy-tetrahydrofuran-2-yl]propyl benzoate2×

Produkt 1

HCID 1371087171-[(2S,4R,5R)-4-allyl-5-(5-amino-2,7-dioxo-6H-thiazolo[4,5-d]pyrimidin-3-yl)tetrahydrofuran-2-yl]propyl benzoateAusbeute 179,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of 1-[(2S,4R,5R)-5-(5-amino-2,7-dioxo-6H-thiazolo[4,5-d]pyrimidin-3-yl)-4-phenoxycarbothioyloxy-tetrahydrofuran-2-yl]propyl benzoate (compound 26e, 1.14 g, 2.0 mmol), 2,2′-azobisisobutyronitrile (168 mg, 1 mmol) and allyl(tributyl)stannane (3.08 mL, 10 mmol) in anhydrous toluene (15 mL) was degassed with argon and then heated with stirring at 80° C. for 4 hours. The resulting mixture was stirred with saturated aqueous NH4F at room temperature for 2 hours and extracted with DCM twice. The combined organic layers were dried over Na2SO4, concentrated in vacuo and the residue was purified by column chromatography on silica gel (eluting with 1:3 EtOAc in petroleum ether) to afford 820 mg of 1-[(2S,4R,5R)-4-allyl-5-(5-amino-2,7-dioxo-6H-thiazolo[4,5-d]pyrimidin-3-yl)tetrahydrofuran-2-yl]propyl benzoate (compound 26f) as a brown solid. MS obsd. (ESI+) [(M+H)+]: 457.

Aufarbeitung

  1. customwas degassed with argon
  2. temperatureheated
  3. stirringThe resulting mixture was stirred with saturated aqueous NH4F at room temperature for 2 hours
  4. extractionextracted with DCM twice
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customthe residue was purified by column chromatography on silica gel (eluting with 1:3 EtOAc in petroleum ether)

Quellen und Nachweise

ORD-Eintrag
ord-5cdf030cb7194ab58cfd9dfc480e080c
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09441008B2

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