Potassium Carbonate → HCID 67182945, compound

HRID 2215917Notes

Reaction equation

HRID 2215917 reaction equation
I[C:2]1[C:10]2[NH:9][C:8]3[CH2:11][CH2:12][NH:13][CH2:14][C:7]=3[C:6]=2[CH:5]=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[CH3:21][C:22]([O:25][C:26]([O:28]C(OC(C)(C)C)=O)=O)([CH3:24])[CH3:23].[CH3:36][N:37](C)C(=O)C>C(Cl)Cl.O.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].[Zn].[C-]#N.[C-]#N.[Zn+2]>[C:22]([O:25][C:26]([N:13]1[CH2:12][CH2:11][C:8]2[NH:9][C:10]3[C:2]([C:36]#[N:37])=[CH:3][CH:4]=[CH:5][C:6]=3[C:7]=2[CH2:14]1)=[O:28])([CH3:24])([CH3:23])[CH3:21]

Participants

10

Reactant 4

HCID 11430Potassium CarbonateHCID 31374DimethylacetamideHCID 90495Di-tert-butyl dicarbonateHCID 21952581HCID 21952581, compound

Product 1

HCID 67182945HCID 67182945, compoundYield 91%

Reagents, catalysts & solvents 5

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
120 °C

Procedure

6-Iodo-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (7.70 g, 25 mmol), tris(dibenzylideneacetone)dipalladium(0) (482 mg, 0.52 mmol), zinc (202 mg, 3.0 mmol), Zn(CN)2 (1.819 g, 15 mmol), and 1,1′-(diphenylphosphino)ferrocene (572 mg, 1.03 mmol) were dissolved in N,N-dimethylacetamide (40 mL). The reaction was heated at 120° C. for 1 h then cooled to room temperature. The reaction mixture was diluted with CH2Cl2, filtered through diatomaceous earth, and concentrated. The crude material was dissolved in THF (15 mL) and water (3 mL) and treated with K2CO3 (3.74 g, 27 mmol) and (Boc)2O (5.91 g, 27 mmol). After 2 h, the reaction was diluted with water and extracted with CH2Cl2 (4×20 mL). The combined CH2Cl2 layers were dried over Na2SO4, filtered, and concentrated. The crude material was purified by flash column chromatography (silica gel, 5–25% EtOAc/hexanes) to afford 6-cyano-1,3,4,5-tetrahydro-pyrido[4,3-b]indole-2-carboxylic acid tert-butyl ester (5.24 g, 91%) as an oil.

Workup

  1. temperaturethen cooled to room temperature
  2. filtrationfiltered through diatomaceous earth
  3. concentrationconcentrated
  4. dissolutionThe crude material was dissolved in THF (15 mL)
  5. extractionextracted with CH2Cl2 (4×20 mL)
  6. dry with materialThe combined CH2Cl2 layers were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude material was purified by flash column chromatography (silica gel, 5–25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-09a905cddf764d3083ddd8dce6838b57
Source dataset
uspto-grants-2006_09
Patent number
US07109339B2

Reaction notes

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