Potassium Carbonate → HCID 58266442, compound

HRID 1505986Notes

Reaction equation

HRID 1505986 reaction equation
[CH2:1]([N:3]1[CH2:8][CH2:7][C:6](=[CH2:9])[CH2:5][CH2:4]1)[CH3:2].C12BC(CCC1)CCC2.[C:19]1([S:25]([N:28]2[C:32]3[CH:33]=[N:34][C:35]([C:38]#[N:39])=[C:36](Br)[C:31]=3[C:30]3[CH:40]=[CH:41][CH:42]=[N:43][C:29]2=3)(=[O:27])=[O:26])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(=O)([O-])[O-].[K+].[K+]>O.CN(C)C=O.Cl[Pd]Cl.C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:19]1([S:25]([N:28]2[C:32]3[CH:33]=[N:34][C:35]([C:38]#[N:39])=[C:36]([CH2:9][CH:6]4[CH2:7][CH2:8][N:3]([CH2:1][CH3:2])[CH2:4][CH2:5]4)[C:31]=3[C:30]3[CH:40]=[CH:41][CH:42]=[N:43][C:29]2=3)(=[O:27])=[O:26])[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 789669-Borabicyclo(3.3.1)nonaneHCID 21063990HCID 21063990, compoundHCID 58266792HCID 58266792, compound

Product 1

HCID 58266442HCID 58266442, compoundYield 43.5%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
65 °C

Procedure

A mixture of 1-ethyl-4-methylene-piperidine (540 mg, 4.32 mmol) and 9-borabicyclo[3.3.1]nonane (0.5M in THF, 8.0 mL, 4.0 mmol) was heated at 65° C. for 3.5 h. The resultant cooled solution was then added portionwise to a degassed suspension of 9-benzenesulfonyl-5-bromo-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (420 mg, 1 mmol), bis(diphenylphosphino)ferrocene dichloropalladium(II) (90 mg, 0.11 mmol) and potassium carbonate (180 mg, 1.3 mmol) in water (1 mL) and dimethylformamide (10 mL). The resultant orange solution was heated at 65° C. for 2 h then allowed to cool to ambient temperature and partitioned between dichloromethane (20 mL) and a saturated aqueous solution of sodium chloride (15 mL). The aqueous phase was extracted with dichloromethane (3×10 mL) and the combined organic phase was washed with a saturated aqueous solution of sodium chloride (20 mL), dried over magnesium sulfate and concentrated in vacuo. The resultant residue was purified by flash chromatography (silica, 10 g column, Si-SPE, 0-20% MeOH in DCM) to afford the title compound (200 mg, 43%). 1H NMR (CDCl3, 400 MHz): 9.81 (s, 1H), 8.76 (dd, J=4.8, 1.5 Hz, 1H), 8.66 (d, J=8.0 Hz, 1H), 8.29-8.24 (m, 2H), 7.66-7.60 (m, 1H), 7.58-7.48 (m, 3H), 3.41 (d, J=7.2 Hz, 2H), 2.89 (q, J=7.3 Hz, 2H), 2.56-2.44 (m, 2H), 2.33-2.08 (m, 3H), 1.94-1.74 (m, 4H), 1.35 (t, J=7.3 Hz, 3H). LCMS (Method G): RT=3.01 min, M+H+=460.

Workup

  1. temperatureThe resultant cooled solution
  2. temperatureThe resultant orange solution was heated at 65° C. for 2 h
  3. temperatureto cool to ambient temperature
  4. custompartitioned between dichloromethane (20 mL)
  5. extractionThe aqueous phase was extracted with dichloromethane (3×10 mL)
  6. washthe combined organic phase was washed with a saturated aqueous solution of sodium chloride (20 mL)
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe resultant residue was purified by flash chromatography (silica, 10 g column, Si-SPE, 0-20% MeOH in DCM)

Sources & evidence

ORD record
ord-35105eca17574eeca9728425b55163a5
Source dataset
uspto-grants-2015_12
Patent number
US09216980B2

Reaction notes

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