Water → HCID 64521714, compound

HRID 1504537Notes

Reaction equation

HRID 1504537 reaction equation
[F:1][C:2]1[CH:3]=[C:4](B(O)O)[CH:5]=[CH:6][CH:7]=1.C(=O)([O-])[O-].[Na+].[Na+].[C:17]1(=[O:22])[CH2:21][CH2:20][CH:19]=[CH:18]1.O>CCCCCCC.C1CC=CCCC=C1.C1CC=CCCC=C1.[Cl-].[Cl-].[Rh].[Rh].C(Cl)Cl.CCOC(C)=O>[F:1][C:2]1[CH:3]=[C:4]([CH:19]2[CH2:20][CH2:21][C:17](=[O:22])[CH2:18]2)[CH:5]=[CH:6][CH:7]=1

Participants

9

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 135882-Cyclopenten-1-oneHCID 27339863-Fluorophenylboronic acid

Product 1

HCID 64521714HCID 64521714, compoundYield 61.6%

Reagents, catalysts & solvents 4

HCID 6436379Rhodium, di-mu-chlorobis((1,2,5,6-eta)-1,5-cyclooctadiene)di-CatalystHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent2×HCID 8900HeptaneSolvent

Conditions

Temperature
90 °C

Procedure

A 40 mL vial was charged with (3-fluorophenyl)boronic acid (1.278 g, 9.14 mmol) and purged with nitrogen for 10 min. The reaction vessel was then sequentially charged with dioxane (15.2 mL), an aqueous solution of sodium carbonate (5.1 mL, 1.9 M), and 2-cyclopenten-1-one (0.510 ml, 6.09 mmol) via syringe. Chloro(1,5-cyclooctadiene)rhodium (I) dimer (0.090 g, 0.183 mmol) was introduced in a single portion. The vial was sealed with a PTFE line cap and the resultant reaction mixture was heated to 90° C. After 2 h, the reaction mixture was allowed to cool to RT and poured into a mixture of water (30 mL) and EtOAc (30 mL). The layers were separated and the aqueous layer was extracted with EtOAc (2×30 mL). The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography (50-g Biotage column, eluent: gradient, 0 to 100% EtOAc in heptane with 10% CH2Cl2 as an additive) to afford 3-(3-fluorophenyl)cyclopentanone (668 mg, 3.75 mmol, 61.6% yield) as a clear oil. 1H NMR (400 MHz, CHLOROFORM-d) δ=7.37-7.23 (m, 1H), 7.08-6.99 (m, 1H), 6.99-6.89 (m, 1H), 3.50-3.33 (m, 1H), 2.68 (dd, J=7.7, 18.3 Hz, 1H), 2.53-2.40 (m, 2H), 2.39-2.25 (m, 2H), 2.05-1.90 (m, 1H). m/z (ESI) 179.2 (+H)+.

Workup

  1. custompurged with nitrogen for 10 min
  2. additionThe reaction vessel was then sequentially charged with dioxane (15.2 mL)
  3. customcap
  4. customthe resultant reaction mixture
  5. temperatureto cool to RT
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with EtOAc (2×30 mL)
  8. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by flash column chromatography (50-g Biotage column, eluent

Sources & evidence

ORD record
ord-594f0e939cc845a08e9c130ca06bdd03
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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