Tri-o-tolylphosphine → 5-(2-Benzyloxy-4-vinylphenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one

HRID 1642609Notes

Reaction equation

HRID 1642609 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[C:13](I)[CH:12]=[CH:11][C:10]=1[N:16]1[S:20](=[O:22])(=[O:21])[N:19]([CH2:23][CH2:24][Si:25]([CH3:28])([CH3:27])[CH3:26])[C:18](=[O:29])[CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:30]([Sn](CCCC)(CCCC)C=C)[CH2:31]CC.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[F-].[K+]>C(#N)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([CH:30]=[CH2:31])[CH:12]=[CH:11][C:10]=1[N:16]1[S:20](=[O:22])(=[O:21])[N:19]([CH2:23][CH2:24][Si:25]([CH3:28])([CH3:27])[CH3:26])[C:18](=[O:29])[CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 80271Tri-o-tolylphosphineHCID 81998TributylvinyltinHCID 522689Potassium FluorideHCID 667569375-(2-Benzyloxy-4-iodophenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one

Product 1

HCID 667565425-(2-Benzyloxy-4-vinylphenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 5-(2-benzyloxy-4-iodophenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one (2.24 g, 4.1 mmol) in acetonitrile (41 mL), in a pressure vessel, is added tributyl(vinyl)tin (1.43 mL, 4.9 mmol), Pd2(dba)3 (73 mg, 0.16 mmol), and tri-o-tolylphosphine. The vessel is sealed and the mixture is stirred at 80° C. for 18 h. The reaction is allowed to cool to ambient temperature, then stirred vigorously with saturated KF (10 mL) for 15 min. The mixture is filtered through Celite, washing several times with acetonitrile. The solvent is removed under reduced pressure and the crude residue is purified via silica gel chromatography using a gradient of 0-40% EtOAc/hexanes to afford 5-(2-benzyloxy-4-vinylphenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one as a colorless oil: MS (M+NH4)+=462.

Workup

  1. customThe vessel is sealed
  2. temperatureto cool to ambient temperature
  3. filtrationThe mixture is filtered through Celite
  4. washwashing several times with acetonitrile
  5. customThe solvent is removed under reduced pressure
  6. customthe crude residue is purified via silica gel chromatography

Sources & evidence

ORD record
ord-22197ccf7333478a89ae30b1452ed729
Source dataset
uspto-grants-2012_02
Patent number
US08119666B2

Reaction notes

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