trans-1-Methoxy-3-trimethylsilyloxy-1,3-butadiene → 1-(2-trimethylsilyl-ethanesulfonyl)-2,3-dihydro-1H-[2,3']bipyridinyl-4-one

HRID 1691832Notes

Reaction equation

HRID 1691832 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH:7]=[N:8][S:9]([CH2:12][CH2:13][Si:14]([CH3:17])([CH3:16])[CH3:15])(=[O:11])=[O:10])[CH:2]=1.CO/[CH:20]=[CH:21]/[C:22]([O:24][Si](C)(C)C)=[CH2:23]>C1(C)C=CC=CC=1>[CH3:15][Si:14]([CH3:17])([CH3:16])[CH2:13][CH2:12][S:9]([N:8]1[CH:20]=[CH:21][C:22](=[O:24])[CH2:23][CH:7]1[C:3]1[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=1)(=[O:11])=[O:10]

Participants

4

Reactant 2

HCID 5366448trans-1-Methoxy-3-trimethylsilyloxy-1,3-butadieneHCID 669074992-Trimethylsilyl-ethanesulfonic acid pyridin-3-ylmethyleneamide

Product 1

HCID 593777611-(2-trimethylsilyl-ethanesulfonyl)-2,3-dihydro-1H-[2,3']bipyridinyl-4-oneYield 40%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 2-trimethylsilyl-ethanesulfonic acid pyridin-3-ylmethyleneamide (665 mg) in toluene (4.5 mL) was added Danishefsky's diene (0.46 mL, 2.4 mmol) under Ar atmosphere. The mixture was heated at reflux for 90 minutes. The toluene was removed in vacuo and the residue was dissolved in dichloromethane (ca. 10 mL) and treated with 2N HCl (ca. 10 mL) for 5 minutes. 10% Aqueous sodium bicarbonate was added carefully to adjust to pH 8. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic extracts were dried (Na2SO4), filtered and evaporated to dryness under reduced pressure. Purification of the residue by flash chromatography (gradient hexane/ethyl acetate) gave 1-(2-trimethylsilyl-ethanesulfonyl)-2,3-dihydro-1H-[2,3′]bipyridinyl-4-one (322 mg, 40% overall).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 90 minutes
  3. customThe toluene was removed in vacuo
  4. dissolutionthe residue was dissolved in dichloromethane (ca. 10 mL)
  5. additiontreated with 2N HCl (ca. 10 mL) for 5 minutes
  6. addition10% Aqueous sodium bicarbonate was added carefully
  7. customThe phases were separated
  8. extractionthe aqueous phase was extracted with dichloromethane
  9. dry with materialThe combined organic extracts were dried (Na2SO4)
  10. filtrationfiltered
  11. customevaporated to dryness under reduced pressure
  12. customPurification of the residue by flash chromatography (gradient hexane/ethyl acetate)

Sources & evidence

ORD record
ord-38e7220ae01b4dd0a0d01cb1ec3efad7
Source dataset
uspto-grants-2012_04
Patent number
US08153809B2

Reaction notes

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