Triphenylphosphine → HCID 67116105, compound

HRID 444700Notes

Reaction equation

HRID 444700 reaction equation
[Br:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1/[C:7](/[NH:17][CH:18]([C:20]1[S:21][CH:22]=[CH:23][N:24]=1)[CH3:19])=[C:8](\[C:15]#[N:16])/[C:9]([O:11]CC=C)=[O:10].N1CCCC1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1/[C:7](/[NH:17][CH:18]([C:20]1[S:21][CH:22]=[CH:23][N:24]=1)[CH3:19])=[C:8](\[C:15]#[N:16])/[C:9]([OH:11])=[O:10]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 67116163HCID 67116163, compound

Product 1

HCID 67116105HCID 67116105, compoundYield 92.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

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.

Workup

  1. customThe reaction medium was quenched with aqueous HCl 1N (5 ml)
  2. additiondiluted with water
  3. extractionwas extracted again with aqueous 1N NaOH
  4. extractionextracted with DCM (CH2Cl2)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-118905ca87a242f49fb0d4109023bc68
Source dataset
uspto-grants-2013_07
Patent number
US08476197B2

Reaction notes

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