Triethylamine → HCID 66763894, compound

HRID 467496Notes

Reaction equation

HRID 467496 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)#[CH:2].I[C:10]1[C:18]2[C:13](=[N:14][CH:15]=[C:16]([C:19]3[CH:24]=[CH:23][C:22]([S:25]([CH:28]([CH3:30])[CH3:29])(=[O:27])=[O:26])=[CH:21][CH:20]=3)[N:17]=2)[N:12]([S:31]([C:34]2[CH:39]=[CH:38][C:37]([CH3:40])=[CH:36][CH:35]=2)(=[O:33])=[O:32])[CH:11]=1.C(N(CC)CC)C>CN(C=O)C.[Cu]I.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>[CH:28]([S:25]([C:22]1[CH:23]=[CH:24][C:19]([C:16]2[N:17]=[C:18]3[C:10]([C:2]#[C:1][C:3]4[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=4)=[CH:11][N:12]([S:31]([C:34]4[CH:39]=[CH:38][C:37]([CH3:40])=[CH:36][CH:35]=4)(=[O:33])=[O:32])[C:13]3=[N:14][CH:15]=2)=[CH:20][CH:21]=1)(=[O:27])=[O:26])([CH3:30])[CH3:29]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 667631397-Iodo-2-(4-isopropylsulfonylphenyl)-5-(p-tolylsulfonyl)pyrrolo[2,3-b]pyrazine

Product 1

HCID 66763894HCID 66763894, compoundYield 67.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

Ethynylbenzene (34.26 mg, 36.92 μL, 0.3354 mmol) was added dropwise to a stirred solution of 7-iodo-2-(4-isopropylsulfonylphenyl)-5-(p-tolylsulfonyl)pyrrolo[2,3-b]pyrazine (150 mg, 0.2580 mmol), triethylamine (130.5 mg, 179.8 μL, 1.290 mmol), copper(I) iodide (5.896 mg, 0.03096 mmol) and Pd(PPh3)4 (14.91 mg, 0.01290 mmol) in DMF (1.3 mL) and the resulting solution stirred at ambient temperature for 64 hours. The solution was added dropwise to a mixture of EtOAc/ice water and the layers separated. The organic layer was washed with brine (×2), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (ISCO Companion™, 12 g column, eluting with 2 to 20% EtOAc/DCM, loaded in DCM) to give the sub-title product as an off-white solid (96.4 mg, 67% Yield). 1H NMR (400.0 MHz, DMSO) δ 1.19 (d, 6H), 2.38 (s, 3H), 3.49 (s, 1H), 7.50 (t, 5H), 7.64 (t, 2H), 8.01 (d, 2H), 8.10 (d, 2H), 8.44 (d, 2H), 8.81 (s, 1H) and 9.24 (s, 1H) ppm; MS (ES+) 556.1.

Workup

  1. customthe layers separated
  2. washThe organic layer was washed with brine (×2)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by column chromatography (ISCO Companion™, 12 g column, eluting with 2 to 20% EtOAc/DCM, loaded in DCM)

Sources & evidence

ORD record
ord-c728b00ec50446fd9fd5ade4c3f0a2a0
Source dataset
uspto-grants-2014_01
Patent number
US08623869B2

Reaction notes

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