2-Bromopyrimidine → 3-((e)-2-(Pyrimidin-2-yl)vinyl)-5,5,8,8,-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde

HRID 1836913Notes

Reaction equation

HRID 1836913 reaction equation
Br[C:2]1[C:3]([CH:16]=[O:17])=[CH:4][C:5]2[C:6]([CH3:15])([CH3:14])[CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]=2[CH:11]=1.C([Sn](C[CH2:43][CH2:44][CH3:45])(CCCC)/C=C/[Sn](CCCC)(CCCC)CCCC)CCC.BrC1[N:52]=[CH:51][CH:50]=[CH:49][N:48]=1>C1(C)C=CC=CC=1.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>[N:48]1[CH:49]=[CH:50][CH:51]=[N:52][C:43]=1/[CH:44]=[CH:45]/[C:2]1[C:3]([CH:16]=[O:17])=[CH:4][C:5]2[C:6]([CH3:15])([CH3:14])[CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]=2[CH:11]=1

Participants

6

Reactant 3

HCID 783452-BromopyrimidineHCID 5378370trans-1,2-Bis(tri-n-butylstannyl)ethyleneHCID 177898873-Bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde

Product 1

HCID 234988743-((e)-2-(Pyrimidin-2-yl)vinyl)-5,5,8,8,-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehydeYield 27%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 1140TolueneSolvent2×

Procedure

A solution of 0.874 g (2.96 mmol) of 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde, 1.886 g (3.11 mmol) of trans-1,2-bis(tri-n-butylstannyl)ethylene and 0.068 g (0.059 mmol) of tetrakis(triphenylphosphine)palladium in 20 ml toluene was heated to reflux under argon for 1.75 hour. The reaction was cooled slightly and 0.518 g (3.26 mmol) of 2-bromopyrimidine and 0.068 g (0.059 mmol) of tetrakis(triphenylphosphine)palladium was added in 3.5 ml toluene. The reaction was heated at reflux for 3 hours. The reaction was cooled to room temperature, quenched with 5% potassium fluoride and diluted with ethyl acetate. The two phases were stirred vigorously for 16 hours. The mixture was filtered through celite and the organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude material was purified by flash chromatography (gradient elution with 20% ethyl acetate/hexane-25% ethyl acetate/hexane) to afford 0.254 g (27%) of 3-((E)-2-(pyrimidin-2-yl)vinyl)-5,5,8,8,-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde (M+1=321).

Workup

  1. temperatureto reflux under argon for 1.75 hour
  2. temperatureThe reaction was cooled slightly
  3. temperatureThe reaction was heated
  4. temperatureat reflux for 3 hours
  5. customquenched with 5% potassium fluoride
  6. additiondiluted with ethyl acetate
  7. filtrationThe mixture was filtered through celite
  8. washthe organic layer was washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated in vacuo
  11. customThe crude material was purified by flash chromatography (gradient elution with 20% ethyl acetate/hexane-25% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-fb9e110f1f6d4e1fa68c255be40b133b
Source dataset
uspto-grants-2004_08
Patent number
US06777418B2

Reaction notes

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