Dichloromethane → (R)-methyl 4-(2-(3-((tert-butyldimethylsilyl)oxy)-5-oxocyclopent-1-en-1-yl)ethyl)benzoate

HRID 1053798Notes

Reaction equation

HRID 1053798 reaction equation
B1C2CCCC1CCC2.[CH:10]([C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=1)=[CH2:11].[Si:22]([O:29][C@@H:30]1[CH2:34][C:33](=[O:35])[C:32](I)=[CH:31]1)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23].C(Cl)Cl.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1COCC1.CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Si:22]([O:29][C@@H:30]1[CH2:34][C:33](=[O:35])[C:32]([CH2:11][CH2:10][C:12]2[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=2)=[CH:31]1)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23]

Participants

9

Reactant 5

HCID 6344DichloromethaneHCID 62657Potassium Phosphate, TribasicHCID 789669-Borabicyclo(3.3.1)nonaneHCID 583124Methyl 4-ethenylbenzoateHCID 11099812(R)-4-(tert-Butyl-dimethyl-silanyloxy)-2-iodo-cyclopent-2-enone

Product 1

HCID 131736290(R)-methyl 4-(2-(3-((tert-butyldimethylsilyl)oxy)-5-oxocyclopent-1-en-1-yl)ethyl)benzoateYield 75.8%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 9-BBN (6.95 g, 28.5 mmol) in 110 mL THF was cannula transferred to a solution of methyl 4-vinylbenzoate (4.65 g, 28.7 mmol) in 22 mL THF, rinsing with 10 mL THF. The reaction was stirred at room temperature for 4 h, was cooled to 0° C. and 5.4 mL H2O was added. After 45 minutes at room temperature, the solution was cannula transferred to a mixture of the (R)-4-((tert-butyldimethylsilyl)oxy)-2-iodocyclopent-2-enone (8 g, 24 mmol) and PdCl2(dppf).CH2Cl2 (1.76 g, 2.41 mmol) in DMF (70 mL). The reaction was stirred for 5 minutes and then a solution of K3PO4 (9.6 mL, 28.8 mmol, 3 M) was added. The resulting dark mixture was allowed to stir overnight and then was partitioned between ethyl acetate/H2O. The organic solution was washed further with H2O (2×) and brine and then was dried (Na2SO4), filtered and evaporated. Purification by flash chromatography (ethyl acetate/hexanes) gave the title compound (6.81 g).

Workup

  1. washrinsing with 10 mL THF
  2. temperaturewas cooled to 0° C.
  3. addition5.4 mL H2O was added
  4. waitAfter 45 minutes at room temperature
  5. stirringThe reaction was stirred for 5 minutes
  6. stirringto stir overnight
  7. customwas partitioned between ethyl acetate/H2O
  8. washThe organic solution was washed further with H2O (2×) and brine
  9. dry with materialwas dried (Na2SO4)
  10. filtrationfiltered
  11. customevaporated
  12. customPurification by flash chromatography (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-c62d47836c6e4d038231afea7388f5cd
Source dataset
uspto-grants-2016_07
Patent number
US09394273B2

Reaction notes

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