Sodium Fluoride → HCID 53752613, compound

HRID 369116Notes

Reaction equation

HRID 369116 reaction equation
[C:1]1([CH:7]2[CH2:12][CH2:11][N:10]([CH2:13][C:14]([Sn](CCCC)(CCCC)CCCC)=[CH:15][CH2:16][N:17]([CH3:27])[S:18]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)(=[O:20])=[O:19])[CH2:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)([O-])[O-].[K+].[K+].Br[C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1.[F-].[Na+]>CN1CCCC1=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:48]1([C:14]([CH2:13][N:10]2[CH2:11][CH2:12][CH:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[CH2:8][CH2:9]2)=[CH:15][CH2:16][N:17]([CH3:27])[S:18]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)(=[O:20])=[O:19])[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1

Participants

7

Reactant 4

HCID 5235Sodium FluorideHCID 7961BromobenzeneHCID 11430Potassium CarbonateHCID 70262325HCID 70262325, compound

Product 1

HCID 53752613HCID 53752613, compoundYield 70.4%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
70 °C

Procedure

To 250 mg (0.37 mmol) of N-[4-(4-phenylpiperidin-1-yl)-3-tributylstannylbut-2-en-1-yl]-N-methylbenzenesulfonamide from Example 21, Step B (isomeric higher Rf product) in 0.5 mL of N-methylpyrrolidinone under argon was added 75 mg (0.55 mmol) of potassium carbonate, 8 mg (2% cat) of dichlorobis(triphenylphosphine)-palladium (II) and 90 mg (0.55 mmol) of bromobenzene. The mixture was heated at 70° C. for 24 h, cooled, treated with aqueous sodium fluoride for 10 min, and partitioned between water and ether. The water layer was reextracted with ether and each organic layer was washed with brine, dried over sodium sulfate, combined and concentrated in vacuo. The residue was purified by FCC eluting with 20-25% ethyl acetate/hexanes to give 120 mg of title product as an oil. 1H NMR (400 MHz, CDCl3): δ 1.55-1.6 (m, 2H), 2.75 (br d, J=11, 2H), 2.00 (br dt, J=2 and 14, 2H), 2.42 (m, 1H), 2.78 (s, 3H), 2.93 (br d, J=11, 2H), 3.33 (s, 2H), 4.05 (d, J=6.5, 2H), 5.78 (t, J=6.5, 1H), 7.1-7.4 (3 m, 5H), 7.5-7.65 (m, 3H), 7.84 (dd, J=1.5 and 7, 2H). Mass spectrum (ESI): m/z 461 (M+1, 100%).

Workup

  1. temperaturecooled
  2. custompartitioned between water and ether
  3. washeach organic layer was washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by FCC
  7. washeluting with 20-25% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-e82f935d2dd44e0794b3618d43063c3b
Source dataset
uspto-grants-2000_10
Patent number
US06136827

Reaction notes

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