Acetylene → HCID 68282833, compound

HRID 1473095Notes

Reaction equation

HRID 1473095 reaction equation
Cl[C:2]1[C:7]([C:8]([F:11])([F:10])[F:9])=[CH:6][N:5]=[C:4]([NH:12][C:13]2[CH:18]=[CH:17][C:16]([N:19]3[CH2:24][CH2:23][CH:22]([NH:25][C:26](=[O:32])[O:27][C:28]([CH3:31])([CH3:30])[CH3:29])[CH2:21][CH2:20]3)=[CH:15][CH:14]=2)[N:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[C:59]([C:61]1[CH:66]=[CH:65][CH:64]=[CH:63][C:62]=1[CH2:67][C:68]([O:70][CH3:71])=[O:69])#[CH:60].C#C>CN(C=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:28]([O:27][C:26]([NH:25][CH:22]1[CH2:23][CH2:24][N:19]([C:16]2[CH:17]=[CH:18][C:13]([NH:12][C:4]3[N:3]=[C:2]([C:60]#[C:59][C:61]4[CH:66]=[CH:65][CH:64]=[CH:63][C:62]=4[CH2:67][C:68]([O:70][CH3:71])=[O:69])[C:7]([C:8]([F:11])([F:10])[F:9])=[CH:6][N:5]=3)=[CH:14][CH:15]=2)[CH2:20][CH2:21]1)=[O:32])([CH3:31])([CH3:30])[CH3:29]

Participants

9

Reactant 5

HCID 6326AcetyleneHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 45789861Methyl 2-(2-ethynylphenyl)acetateHCID 86675723HCID 86675723, compound

Product 1

HCID 68282833HCID 68282833, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

A suspension of tert-butyl (1-(4-((4-chloro-5-(trifluoromethyl)pyrimidin-2-yl)amino)phenyl)piperidin-4-yl)carbamate (I76) (550 mg, 1.17 mmol), CuI (15 mg, 0.12 mmol), triphenylphosphine (31 mg, 0.117 mmol) and triethylamine (487 μL, 3.50 mmol) in DMF (6 mL) was sonicated for 5 minutes in a 10 mL microwave vial, to this PdCl2(PPh3)2 (54.0 mg, 0.077 mmol) and methyl 2-(2-ethynylphenyl)acetate (I4) (305 mg, 1.75 mmol) were added and the reaction heated to 120° C. for 20 minutes under microwave irradiation. Upon cooling the reaction mixture was chromatographed on silica gel using gradient elution (0-100% ethyl acetate in petroleum benzine 40-60° C.) to yield a mixture of the title compound (I77) and homo-coupled acetylene which was used without further purification.

Workup

  1. additionwere added
  2. temperatureUpon cooling the reaction mixture
  3. customwas chromatographed on silica gel using gradient elution (0-100% ethyl acetate in petroleum benzine 40-60° C.)
  4. customto yield

Sources & evidence

ORD record
ord-4a84b7a3eb4d4eaebcddd4f258a9df93
Source dataset
uspto-grants-2015_04
Patent number
US09012461B2

Reaction notes

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