2-(Trimethylsilylmethyl)allyl acetate → Methyl (+-)-trans-4-methylene-2-(3-fluorophenyl)cyclopentanoate

HRID 993220Notes

Reaction equation

HRID 993220 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][CH:13]=1)/[CH:5]=[CH:6]/[C:7]([O:9][CH3:10])=[O:8].C(O[CH2:18][C:19]([CH2:21][Si](C)(C)C)=[CH2:20])(=O)C>C1COCC1.CCCCCC.[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.C1(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:18]=[C:19]1[CH2:21][C@@H:6]([C:7]([O:9][CH3:10])=[O:8])[C@H:5]([C:4]2[CH:11]=[CH:12][CH:13]=[C:2]([F:1])[CH:3]=2)[CH2:20]1

Participants

7

Reactant 2

HCID 44283472-(Trimethylsilylmethyl)allyl acetateHCID 13415099Methyl (E)-3-fluorocinnamate

Product 1

HCID 53991082Methyl (+-)-trans-4-methylene-2-(3-fluorophenyl)cyclopentanoateYield 83.9%

Reagents, catalysts & solvents 4

HCID 742671,2-Bis(diphenylphosphino)ethaneCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A mixture of methyl trans-3-fluorocinnamate (41.25 g, 229 mmol), tetrakis(triphenylphosphine) palladium(0) (18.5 g, 16 mmol), 1,2-bis(diphenylphosphino)ethane (5.5 g, 13.7 mmol) and 2-((trimethylsilyl)methyl)-2-propen-1-yl acetate (42.66 g, 229 mmol) in THF (300 mL) under nitrogen was heated to reflux for 6 h and then stirred at rt for 16 h. The reaction was diluted with hexane and filtered to remove yellow precipitate. The volatiles were then removed in vacuo and the residue was purified by FC (3 to 5% ethyl acetate in hexanes) to afford the title compound (45 g).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 6 h
  3. filtrationfiltered
  4. customto remove yellow precipitate
  5. customThe volatiles were then removed in vacuo
  6. customthe residue was purified by FC (3 to 5% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-589f968080b0467ba8c778612e5c528a
Source dataset
uspto-grants-2002_10
Patent number
US06472410B1

Reaction notes

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