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

Reaction equation

HRID 60734 reaction equation
[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

Participants

5

Reactant 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×

Product 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 benzoateYield 179.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

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.

Workup

  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)

Sources & evidence

ORD record
ord-5cdf030cb7194ab58cfd9dfc480e080c
Source dataset
uspto-grants-2016_09
Patent number
US09441008B2

Linked notes

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