Trimethylsilylacetylene → N-methyl-5-(2-(trimethylsilyl)ethynyl)pyrimidin-2-amine

HRID 1042739Notes

Reaction equation

HRID 1042739 reaction equation
F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.C(N(C(C)C)CC)(C)C.Br[C:29]1[CH:30]=[N:31][C:32]([NH:35][CH3:36])=[N:33][CH:34]=1.[CH3:37][Si:38]([C:41]#[CH:42])([CH3:40])[CH3:39]>CCOC(C)=O.[Cu]I.O1CCOCC1>[CH3:36][NH:35][C:32]1[N:31]=[CH:30][C:29]([C:42]#[C:41][Si:38]([CH3:40])([CH3:39])[CH3:37])=[CH:34][N:33]=1

Participants

8

Reactant 4

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 130981845-Bromo-N-methylpyrimidin-2-amine

Product 1

HCID 68462840N-methyl-5-(2-(trimethylsilyl)ethynyl)pyrimidin-2-amine

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A 100 mL round bottom flask was charged with palladium(bisbenzonitrile)dichloride (0.23 g, 0.61 mmol), trit-butylphosphonium tetrafluoroborate (0.35 g, 1.2 mmol) and copper (I) iodide (0.11 g, 0.61 mmol) under argon. 20 mL dioxane was added, followed by diisopropylethylamine (2.6 mL, 18 mmol), 5-bromo-N-methylpyrimidin-2-amine (2.3 g, 12 mmol), and trimethylsilyl acetylene (3.4 mL, 24 mmol). The reaction was allowed to stir overnight. The cloudy brown mixture was diluted with EtOAc and filtered through a pad of silica gel and concentrated in vacuo to give a brown solid. This was further purified by silica gel chromatography, eluting with 0-50% EtOAc/dichloromethane to give N-methyl-5-(2-(trimethylsilyl)ethynyl)pyrimidin-2-amine as a yellow solid. MS m/z=206 [M+H]+. Calc'd for C10H15N3Si: 205.

Workup

  1. filtrationfiltered through a pad of silica gel
  2. concentrationconcentrated in vacuo
  3. customto give a brown solid
  4. customThis was further purified by silica gel chromatography
  5. washeluting with 0-50% EtOAc/dichloromethane

Sources & evidence

ORD record
ord-bbecd16cad7a45ce8f2a9ae08d11d0cf
Source dataset
uspto-grants-2013_10
Patent number
US08557996B2

Reaction notes

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