Azobisisobutyronitrile → N6-Benzoyl-5'-O-tert-butyldimethylsilyl-2',3'-dideoxy-3'-ethylacrylyladenosine

HRID 55553Notes

Reaction equation

HRID 55553 reaction equation
[C:1]([NH:9][C:10]1[C:11]2[N:12]=[CH:13][N:14]([C:39]=2[N:40]=[CH:41][N:42]=1)[C@@H:15]1[O:38][C@H:28]([CH2:29][O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[C@@H:17](OC(OC2C=CC=CC=2)=S)[CH2:16]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:43]([O:45]C(=O)/C=C\[Sn](CCCC)(CCCC)CCCC)[CH3:44].C[Sn](C)C.C[Sn](C)C.N([C:78]([CH3:82])([CH3:81])C#N)=NC(C)(C)C#N>C1(C)C=CC=CC=1>[C:1]([NH:9][C:10]1[C:11]2[N:12]=[CH:13][N:14]([C:39]=2[N:40]=[CH:41][N:42]=1)[C@@H:15]1[O:38][C@H:28]([CH2:29][O:30][Si:31]([C:34]([CH3:35])([CH3:37])[CH3:36])([CH3:32])[CH3:33])[C@@H:17]([C:43](=[O:45])[CH:44]=[CH:82][CH2:78][CH3:81])[CH2:16]1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 6327618HexamethylditinHCID 10992754Ethyl 3-(tributylstannyl)prop-2-enoateHCID 131720001N6-Benzoyl-5'-O-tert-butyldimethylsilyl-2'-deoxy-3'-O-phenoxythiocarbonyladenosine

Product 1

HCID 131720000N6-Benzoyl-5'-O-tert-butyldimethylsilyl-2',3'-dideoxy-3'-ethylacrylyladenosineYield 44.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
87 °C

Procedure

N6 -Benzoyl-5'-O-tert-butyldimethylsilyl-2,'3'-dideoxy-3'-ethylacrylyladenosine (Compound 10, Table III) was prepared by dissolving N6 -Benzoyl-5'-O-tert-butyldimethylsilyl-2'-deoxy-3'-O-phenoxythiocarbonyladenosine (50 mg, 0.08 mmole), cis-ethyl-3-tributylstannyl-2-propenoate (92 mg, 0.236 mmole) and hexamethylditin (13 mg, 0.04 mmole) in 2 ml toluene in a 40 ml Schlenk tube, and then adding 15 mg (0.11 mmole) azo-bis-isobutyronitrile to the mixture. The resulting mixture was freeze-pump-thaw degassed 3 times and then heated at 87° C. in an oil bath for 3 days. Approximately every 12 hours, fresh 15 mg azo-bisisobutyronitrile was added to the reaction. Following the 3-day incubation period, the reaction was cooled, the solvent evaporated, and the residue chromatographed with 1% ethanol in dichloromethane as eluent. A yield of 19 mg N6 -Benzoyl-5'-O-tert-butyldimethylsilyl-2',3'-dideoxy-3'-ethylacrylyladenosine was obtained as a white solid after evaporation of the appropriate fractions (42% yield).

Workup

  1. customThe resulting mixture was freeze-pump-thaw degassed 3 times
  2. additionfresh 15 mg azo-bisisobutyronitrile was added to the reaction
  3. customthe 3-day
  4. temperaturethe reaction was cooled
  5. customthe solvent evaporated
  6. customthe residue chromatographed with 1% ethanol in dichloromethane as eluent

Sources & evidence

ORD record
ord-da90787e95b8412ca5f3609a02186029
Source dataset
uspto-grants-1997_04
Patent number
US05625050

Reaction notes

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