Acetonitrile → HCID 135530149, compound

HRID 1636008Notes

Reaction equation

HRID 1636008 reaction equation
[CH2:1]([C:3]1[N:4]([CH:24]2[CH2:27][N:26]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:25]2)[N:5]=[C:6]2[C:11](=[O:12])[NH:10][C:9]([C:13]3[C:14]([O:20][CH2:21][CH2:22][CH3:23])=[N:15][CH:16]=[C:17](I)[CH:18]=3)=[N:8][C:7]=12)[CH3:2].[CH3:35][Si:36]([C:39]#[CH:40])([CH3:38])[CH3:37].C(#N)C>C(N(CC)CC)C.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>[CH2:1]([C:3]1[N:4]([CH:24]2[CH2:27][N:26]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:25]2)[N:5]=[C:6]2[C:11](=[O:12])[NH:10][C:9]([C:13]3[C:14]([O:20][CH2:21][CH2:22][CH3:23])=[N:15][CH:16]=[C:17]([C:40]#[C:39][Si:36]([CH3:38])([CH3:37])[CH3:35])[CH:18]=3)=[N:8][C:7]=12)[CH3:2]

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 66111Trimethylsilylacetylene2×HCID 135466604HCID 135466604, compound

Product 1

HCID 135530149HCID 135530149, compound

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

The product from stage e) (0.25 mmol) was suspended in triethylamine (2 ml) and trimethylsilylacetylene (0.39 mmol) and acetonitrile (2 ml to try and solubilise reactants). Pd(PPh3)2Cl2 (0.006 mmol) and cuprous iodide (0.006 mmol) were added and the reaction mixture stirred. After 1 h a further portion of trimethylsilylacetylene (0.19 mmol) was added and stirring continued for 2 h. The solvent was evaporated and the residue partitioned between ethyl acetate and water. The organics were washed with brine, dried (MgSO4) and concentrated. Purification by flash column chromatography (gradient elution from 100% dichloromethane to 99% dichloromethane/methanol) gave the title compound; 1H NMR (400MHz, MeOD): δ=0.25 (s, 9H), 1.05 (t, 3H), 1.31 (t, 3H), 1.44 (s, 9H), 1.87-1.96 (m, 2H), 3.00 (q, 2H), 4.33 (t, 2H), 4.52 (t, 2H), 4.54-4.80 (m, 2H), 5.18-5.25 (m, 1H), 8.32 (d, 1H), 8.74 (d, 1H); LRMS (TSP—positive ion) 569 (MNH4+), 452.0 (MH+); Anal. Found C, 60.82;H, 6.90; N, 15.15 Calcd for C28H38O4N6Si: C, 61.07;H, 6.95; N, 15.26.

Workup

  1. stirringstirring
  2. customThe solvent was evaporated
  3. customthe residue partitioned between ethyl acetate and water
  4. washThe organics were washed with brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customPurification
  8. washby flash column chromatography (gradient elution from 100% dichloromethane to 99% dichloromethane/methanol)

Sources & evidence

ORD record
ord-87996afdce5e4ee595ad4a896fe14016
Source dataset
uspto-grants-2003_01
Patent number
US06512002B2

Reaction notes

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