Ethanol → HCID 22917400, compound

HRID 36964Notes

Reaction equation

HRID 36964 reaction equation
Br[C:2]1[CH2:6][C:5](C)(C)[CH2:4][C:3]=1[Br:9].[F:10][C:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.C(O)C.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:9][C:3]1[CH2:4][CH2:5][CH2:6][C:2]=1[C:14]1[CH:15]=[CH:16][C:11]([F:10])=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 2856454-Fluorophenylboronic acidHCID 138660731,2-Dibromo-4,4-dimethylcyclopentene

Product 1

HCID 22917400HCID 22917400, compoundYield 24.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

Under nitrogen, 1.3 g (5.1 mmol) of 1,2-dibromo-4,4-dimethylcyclopentene (Step 8) was reacted with 600 mg (4.3 mmol) of 4-fluorophenylboronic acid (Lancaster) in 23 mL of toluene, 15 mL of of ethanol, and 10 mL of 2M Na2CO3 in the presence of 250 mg (5 mol %) of Pd(PPh3)4. The reaction was vigorously stirred at reflux overnight and concentrated in vacuo. The residue was dissolved in ethyl acetate and washed with water, dried (Na2SO4), and reconcentrated. Purification by silica gel chromatography (MPLC) with hexane gave 250 mg of 1-(2-bromocyclopenten-1-yl)-4-fluorobenzene (38 in Synthetic Scheme X when R1 and R2 =CH3, R5 =F, and R3, R4, R6 and R7 =H) as a pale yellow oil which was reacted with 200 mg (1.2 mmol) of 4-methylthiophenylboronic acid (Example 1, Step 1) in 5.2 mL of toluene, 3.4 mL of ethanol, and 2.2 mL of 2H Na2CO3 in the presence of 40 mg (5 mol %) of Pd(PPh3)4. The reaction was vigorously stirred at reflux for 6 hours and concentrated in vacuo. The residue was dissolved in ethyl acetate and washed with water, dried (Na2SO4), and reconcentrated. Purification by silica gel chromatography (MPLC) with hexane gave 120 mg of 1-[2-(4-fluorophenyl)-4,4-dimethylcyclopenten-1-]-4-(methylthio)benzene (41 in Synthetic Scheme X when R1 and R2 =CH3, RS=F, R10 =SCH3, and R3, R4, R6, R7, R8, R9, R11, and R12 =H) as an oil: NMR CDCl3) δ1.20 (s, 6H0, 2.42 (s, 3H), 2.63 (s, 4H), 6.90 (t, J=8 Hz, 2H), 7.00-7.18 (m, 4H), 7.30-7.60 (m, 2H).

Workup

  1. temperatureat reflux overnight
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in ethyl acetate
  4. washwashed with water
  5. dry with materialdried (Na2SO4)
  6. customPurification by silica gel chromatography (MPLC) with hexane

Sources & evidence

ORD record
ord-bd3686f3a33b46a699a944e57fc9de09
Source dataset
uspto-grants-1995_05
Patent number
US05418254

Reaction notes

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