Reaction #531882

Reaction equation

Allyl (2Z)-3-(3-bromo-2-thienyl)-2-cyano-3-{[1-(1,3-thiazol-2-yl)ethyl]amino}acrylate

Pyrrolidine

triphenylphosphine

→

(2Z)-3-(3-bromo-2-thienyl)-2-cyano-3-{[1-(1,3-thiazol-2-yl)ethyl]amino}acrylic acid

Yield 92.1%

Solvents

DCM

Conditions

Workup

1. 1
   OtherThe reaction medium was quenched with aqueous HCl 1N (5 ml)
2. 2
   workup.ADDITIONdiluted with water
3. 3
   Extractionwas extracted again with aqueous 1N NaOH
4. 4
   Extractionextracted with DCM (CH2Cl2)
5. 5
   Dryingdried over MgSO4
6. 6
   Concentrationconcentrated under vacuum

Procedure

Allyl (2Z)-3-(3-bromo-2-thienyl)-2-cyano-3-{[1-(1,3-thiazol-2-yl)ethyl]amino}acrylate (0.1 g, 0.212 mmol, 1 eq.) was dissolved in 5 ml of DCM under Argon and cooled to 0° C. Pyrrolidine (0.018 g, 0.255 mmol, 1.2 eq.) added followed by triphenylphosphine (0.010 g, 0.038 mmol, 0.18 eq.) and tetrakis(triphenylphosphine)palladium(0) (0.012 g, 0.011 mmol, 0.05 eq.). The reaction was stirred at 0° C. for 2 h at which point no starting material remained. The reaction medium was quenched with aqueous HCl 1N (5 ml) and diluted with water. The organic layer was basified with aqueous 1N NaOH until pH 9 and was extracted again with aqueous 1N NaOH. The aqueous layers were combined, acidified with aqueous 1N HCl and extracted with DCM (CH2Cl2). The organic layers were combined, dried over MgSO4 and concentrated under vacuum to give (2Z)-3-(3-bromo-2-thienyl)-2-cyano-3-{[1-(1,3-thiazol-2-yl)ethyl]amino}acrylic acid (0.075 g, 87% yield) as a white solid and a mixture of atropoisomers.

Source