(E)-trimethyl(2-(tributylstannyl)vinyl)silane → HCID 68150547, compound

HRID 244311Notes

Reaction equation

HRID 244311 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([CH:8]2[CH2:10][CH2:9]2)[N:5]=[C:4]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:3]=1Br.[CH3:17][Si:18]([CH3:35])([CH3:34])/[CH:19]=[CH:20]/[Sn](CCCC)(CCCC)CCCC>O1CCOCC1.C(OCC)(=O)C.O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[NH2:1][C:2]1[N:7]=[C:6]([CH:8]2[CH2:10][CH2:9]2)[N:5]=[C:4]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:3]=1/[CH:20]=[CH:19]/[Si:18]([CH3:35])([CH3:34])[CH3:17]

Participants

7

Reactant 2

HCID 10949136(E)-trimethyl(2-(tributylstannyl)vinyl)silaneHCID 11414935HCID 11414935, compound

Product 1

HCID 68150547HCID 68150547, compoundYield 57.2%

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

Ethyl 6-amino-5-bromo-2-cyclopropylpyrimidine-4-carboxylate (0.5 g, 1.747 mmol, see WO 2005063721 for preparation) and tetrakis (triphenylphosphine) palladium(0) (0.214 g, 0.185 mmol) were added to a 20 mL Biotage microwave reaction vessel. The vessel was sealed and purged with nitrogen gas. (E)-trimethyl(2(tributylstannyl)vinyl)silane (0.96 g, 2.466 mmol) in dioxane (8.74 ml) was added and the reaction mixture was heated at 120° C. for 6 h. The cooled reaction mixture was diluted with ethyl acetate and water. The organic phase was washed with saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated onto silica. Purification by flash chromatography (SiO2, 0-40% EtOAc:Hex gradient) provided the title compound as a tan solid (0.305 g, 57% yield): mp 99-101° C.; 1H NMR (400 MHz, DMSO-d6) δ 0.12 (s, 9H), 0.85-0.94 (m, 4H), 1.25 (t, J=7.1 Hz, 3H), 1.91 (tt, J=7.0, 5.6 Hz, 1H), 4.20 (q, J=7.1 Hz, 2H), 6.03 (d, J=19.1 Hz, 1H), 6.70 (d, J=19.2 Hz, 1H), 7.01 (s, 2H); ESIMS m/z 306 ([M+H]+), 304 ([M−H]−).

Workup

  1. customThe vessel was sealed
  2. custompurged with nitrogen gas
  3. customThe cooled reaction mixture
  4. washThe organic phase was washed with saturated sodium chloride
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated onto silica
  8. customPurification by flash chromatography (SiO2, 0-40% EtOAc:Hex gradient)

Sources & evidence

ORD record
ord-7b2afb77a99149a384ee2b4c64046f20
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

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