1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 25204103, compound

HRID 1644641Notes

Reaction equation

HRID 1644641 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([S:8]([NH:11][C:12]2[S:13][CH:14]=[CH:15][N:16]=2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.[NH2:59][C:60]1[N:64]([CH3:65])[N:63]=[C:62]([C:66]([CH3:69])([CH3:68])[CH3:67])[CH:61]=1.CC(C)([O-])C.[Na+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:66]([C:62]1[CH:61]=[C:60]([NH:59][C:2]2[CH:7]=[CH:6][C:5]([S:8]([NH:11][C:12]3[S:13][CH:14]=[CH:15][N:16]=3)(=[O:10])=[O:9])=[CH:4][CH:3]=2)[N:64]([CH3:65])[N:63]=1)([CH3:69])([CH3:67])[CH3:68]

Participants

7

Reactant 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 10193184-Iodo-N-(thiazol-2-yl)benzenesulfonamideHCID 27352873-tert-Butyl-1-methyl-1H-pyrazol-5-amineHCID 23676156Sodium t-butoxide

Product 1

HCID 25204103HCID 25204103, compoundYield 76.6%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

To a mixture of 4-iodo-N-thiazol-2-yl-benzenesulfonamide (50 mg, 0.1 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (5 mg, 0.005 mmol, 0.04 equiv), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (10 mg, 0.0016 mmol, 0.12 equiv) and 5-amino-3-tert-butyl-1-methylpyrazole (25 mg, 0.16 mmol, 1.2 equiv) in 1.8 mL of anhydrous 1,4-dioxane was added sodium tert-butoxide (39 mg, 0.41 mmol, 3.0 equiv). The vial was capped, and the reaction mixture was heated 30 min at 150° C. in the microwave. The crude reaction mixture was filtered through celite then concentrated in vacuo. The residue was taken up in chloroform-methanol, concentrated onto celite, and purified via automated flash chromatography (12 g SiO2, gradient from hexanes to ethyl acetate). The appropriate fractions were collected, concentrated in vacuo, then lyophilized from water-acetonitrile to afford the product as an off-white solid (30 mg, 50%).

Workup

  1. customThe vial was capped
  2. customThe crude reaction mixture
  3. filtrationwas filtered through celite
  4. concentrationthen concentrated in vacuo
  5. concentrationconcentrated onto celite
  6. custompurified
  7. customThe appropriate fractions were collected
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e762d69608494a888539d8987e0bc7c3
Source dataset
uspto-grants-2012_02
Patent number
US08124610B2

Reaction notes

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