Potassium Phosphate, Tribasic → HCID 66605182, compound

HRID 2410800Notes

Reaction equation

HRID 2410800 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:11]1[CH:12]=[C:13]([C:30]([O:32][CH3:33])=[O:31])[C:14]2[NH:15][C:16]3[CH:17]=[C:18]([C:24]([O:26][CH:27]([CH3:29])[CH3:28])=[O:25])[CH:19]=[CH:20][C:21]=3[C:22]=2[N:23]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>CC([O-])=O.CC([O-])=O.[Pd+2]>[C:1]1([C:11]2[CH:12]=[C:13]([C:30]([O:32][CH3:33])=[O:31])[C:14]3[NH:15][C:16]4[CH:17]=[C:18]([C:24]([O:26][CH:27]([CH3:28])[CH3:29])=[O:25])[CH:19]=[CH:20][C:21]=4[C:22]=3[N:23]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 66827Phenylboronic AcidHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 86663046HCID 86663046, compound

Product 1

HCID 66605182HCID 66605182, compoundYield 70.3%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
80 °C

Procedure

A flask containing a mixture of phenylboronic acid (0.935 g, 7.67 mmol), 7-isopropyl 4-methyl 2-bromo-5H-pyrido[3,2-b]indole-4,7-dicarboxylate (1.00 g, 2.56 mmol), powdered potassium phosphate tribasic (2.387 g, 11.25 mmol), 2-dicyclohexylphosphino-2′,4′,6′-tri-iso-propyl-1,1′-biphenyl (0.244 g, 0.511 mmol), and Pd(OAc)2 (0.057 g, 0.256 mmol) was flushed with nitrogen. THF (8 mL) was added and the mixture was heated at 80° C. for 3 hr. The mixture was diluted with EtOAc, washed with water, dried with sodium sulfate, and the solvents removed. Silica gel chromatography (step gradient elution with hexane containing 50% to 100% DCM) afforded 7-isopropyl 4-methyl 2-phenyl-5H-pyrido[3,2-b]indole-4,7-dicarboxylate (0.7 g, 1.8 mmol, 68% yield). MS (ESI) m/z 388.99 (M+H). 1H NMR (500 MHz, chloroform-d) δ ppm 9.68 (1H, s), 8.52 (1H, d, J=8.24 Hz), 8.39 (1H, s), 8.30 (1H, s), 8.21 (2H, d, J=7.32 Hz), 8.08 (1H, d, J=8.24 Hz), 7.56 (2H, t, J=7.63 Hz), 7.41-7.51 (1H, m), 5.36 (1H, dt, J=12.51, 6.26 Hz), 4.14 (3H, s), 1.46 (6H, d, J=6.41 Hz).

Workup

  1. additionA flask containing
  2. customwas flushed with nitrogen
  3. additionTHF (8 mL) was added
  4. additionThe mixture was diluted with EtOAc
  5. washwashed with water
  6. dry with materialdried with sodium sulfate
  7. customthe solvents removed
  8. washSilica gel chromatography (step gradient elution with hexane containing 50% to 100% DCM)

Sources & evidence

ORD record
ord-9ea83098eb694d75a49e7df58c9b1f09
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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