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

HRID 8776

Reaction equation

HRID 8776 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 room temperature for 16 h. The reaction was diluted with hexane and filtered to remove the 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 the 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-7a5cb637174d4ad49a54d0c4b3153ed7
Source dataset
uspto-grants-2006_08
Patent number
US07091211B2

Linked notes

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