Tributylstannane → HCID 86651443, compound

HRID 1969313Notes

Reaction equation

HRID 1969313 reaction equation
[C:1]([O:20][CH2:21][C@H:22]1[O:26][C@@H:25]([N:27]2[CH:31]=[C:30]([C:32]#[C:33][CH3:34])[CH:29]=[C:28]2[CH:35]=[O:36])[CH2:24][C@@H:23]1O)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClC(OC1C=CC=CC=1)=S.C([SnH](CCCC)CCCC)CCC.N(C(C)(C)C#N)=NC(C)(C)C#N>C(#N)C.CN(C)C1C=CN=CC=1.C1(C)C=CC=CC=1>[C:1]([O:20][CH2:21][C@H:22]1[O:26][C@@H:25]([N:27]2[CH:31]=[C:30]([C:32]#[C:33][CH3:34])[CH:29]=[C:28]2[CH:35]=[O:36])[CH2:24][CH2:23]1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

8

Reactant 4

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 70498Phenyl thioxochloroformateHCID 86651441HCID 86651441, compound

Product 1

HCID 86651443HCID 86651443, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1140TolueneSolventHCID 6342AcetonitrileSolvent

Procedure

To a solution of 1-(2-deoxy-5-O-trityl-β-D-ribofuranosyl)-4-(1-propynyl)pyrrole-2-carbaldehyde (392 mg, 797 μmol) in acetonitrile were added 4-dimethylaminopyridine (975 mg, 7.98 mmol) and phenyl chlorothioformate (470 μl, 3.40 mmol) in an argon atmosphere, and the reaction mixture was stirred at room temperature. After 23 hours, the reaction solution was concentrated under reduced pressure, and purified by column chromatography on silica gel (50-67% CH2Cl2 in hexane) to give an intermediate (193 mg, containing minor amounts of impurities). To a solution of this intermediate in toluene (10 ml) were added tri-n-butyltin hydride (165 μl, 612 μmol) and α,α′-azobisisobutyronitrile (15 mg, 92 μmol), and the reaction mixture was refluxed for 5 hours in an argon atmosphere. The reaction solution was concentrated under reduced pressure, and the resulting crude product was purified by column chromatography on silica gel (eluent: 50-80% CH2Cl2 in hexane) to give the title product (84 mg, 58%).

Workup

  1. concentrationthe reaction solution was concentrated under reduced pressure
  2. custompurified by column chromatography on silica gel (50-67% CH2Cl2 in hexane)
  3. customto give
  4. additionan intermediate (193 mg, containing minor amounts of impurities)
  5. temperaturethe reaction mixture was refluxed for 5 hours in an argon atmosphere
  6. concentrationThe reaction solution was concentrated under reduced pressure
  7. customthe resulting crude product was purified by column chromatography on silica gel (eluent: 50-80% CH2Cl2 in hexane)

Sources & evidence

ORD record
ord-3f38918b716b44bb813d0459e681ea03
Source dataset
uspto-grants-2013_04
Patent number
US08426569B2

Reaction notes

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