Sodium Carbonate → HCID 131730545, compound

HRID 1972796Notes

Reaction equation

HRID 1972796 reaction equation
C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Br[C:21]1[CH:22]=[C:23]([C:31]2[CH:36]=[CH:35][CH:34]=[C:33]([C:37]([CH3:45])([CH3:44])[O:38][SiH2:39][C:40]([CH3:43])([CH3:42])[CH3:41])[CH:32]=2)[N:24]2[C:29]=1[C:28]([NH2:30])=[N:27][CH:26]=[N:25]2.[CH2:46]([N:53]1[CH:61]=[C:60]2[C:55]([CH:56]=[C:57](B3OC(C)(C)C(C)(C)O3)[CH:58]=[CH:59]2)=[N:54]1)[C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1.C([O-])([O-])=O.[Na+].[Na+]>CC([O-])=O.CC([O-])=O.[Pd+2].O1CCOCC1.C1(C)C=CC=CC=1>[CH2:46]([N:53]1[CH:61]=[C:60]2[C:55]([CH:56]=[C:57]([C:21]3[CH:22]=[C:23]([C:31]4[CH:36]=[CH:35][CH:34]=[C:33]([C:37]([CH3:45])([CH3:44])[O:38][SiH2:39][C:40]([CH3:43])([CH3:41])[CH3:42])[CH:32]=4)[N:24]4[C:29]=3[C:28]([NH2:30])=[N:27][CH:26]=[N:25]4)[CH:58]=[CH:59]2)=[N:54]1)[C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 585293132-benzyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-IndazoleHCID 131730546HCID 131730546, compound

Product 1

HCID 131730545HCID 131730545, compoundYield 66%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

Pd(OAc)2 (11 mg, 0.05 mmol) was suspended in a degassed mixture of 3:2 toluene:dioxane and PPh3 (52 mg, 0.20 mmol) was added. The mixture was stirred for 10 minutes and then the product from step 3 (433 mg, 1.00 mmol) and Intermediate C (434 mg, 1.30 mmol) were added followed by 2.5 mL of 2M aqueous Na2CO3 solution. The mixture was heated to 90° C. overnight. The reaction was allowed to cool to rt and partitioned between water and EtOAc. The layers were separated and the aqueous layer was extracted with EtOAc. The combined organic phases were washed with brine, dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by Isco® (Redi-sep 40, eluting with 75-100% EtOAc/Hexanes) to provide 368 mg (66%) of the title compound as an off-white solid. 1H-NMR (DMSO-d6) 8.44 (s, 1H), 7.98 (s, 1H), 7.84 (s, 1H), 7.82 (m, 1H), 7.74 (d, 1H), 7.56 (s, 1H), 7.50-7.39 (m, 2H), 7.31 (t, 1H), 7.26-7.12 (m, 5H), 7.08 (d, 1H), 7.00, (s, 1H), 5.57 (s, 2H), 4.64 (s, 2H) 0.82 (s, 9H), 0.01 (s, 6H); LC-MS [M+H]+=561.5, RT=3.65 min.

Workup

  1. temperatureto cool to rt
  2. custompartitioned between water and EtOAc
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with EtOAc
  5. washThe combined organic phases were washed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by Isco® (Redi-sep 40, eluting with 75-100% EtOAc/Hexanes)

Sources & evidence

ORD record
ord-b883d89023264d90b9e650bc5f35db4f
Source dataset
uspto-grants-2013_04
Patent number
US08431695B2

Reaction notes

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