Potassium Phosphate, Tribasic → (e)-2,3,4,5-Tetrahydro-2,8-dimethyl-5-(2-(pyridin-3-yl)prop-1-enyl)-1h-pyrido[4,3-b]indole

HRID 1401521Notes

Reaction equation

HRID 1401521 reaction equation
[CH3:1][N:2]1[CH2:15][CH2:14][C:5]2[NH:6][C:7]3[CH:8]=[CH:9][C:10]([CH3:13])=[CH:11][C:12]=3[C:4]=2[CH2:3]1.N1CCC[C@H]1C(O)=O.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Br[CH:33]=[C:34]([C:36]1[CH:37]=[N:38][CH:39]=[CH:40][CH:41]=1)[CH3:35]>CN(C=O)C.[Cu]I>[CH3:1][N:2]1[CH2:15][CH2:14][C:5]2[N:6](/[CH:33]=[C:34](/[C:36]3[CH:37]=[N:38][CH:39]=[CH:40][CH:41]=3)\[CH3:35])[C:7]3[CH:8]=[CH:9][C:10]([CH3:13])=[CH:11][C:12]=3[C:4]=2[CH2:3]1

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 145742L-ProlineHCID 2092911H-Pyrido[4,3-b]indole, 2,3,4,5-tetrahydro-2,8-dimethyl-HCID 571825283-(1-Bromoprop-1-en-2-yl)pyridine

Product 1

HCID 46199889(e)-2,3,4,5-Tetrahydro-2,8-dimethyl-5-(2-(pyridin-3-yl)prop-1-enyl)-1h-pyrido[4,3-b]indole

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Procedure

2,8-Dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (600 mg, 3 mmol) was dissolved in DMF (12 mL). Copper (I) iodide (114 mg, 0.6 mmol), L-proline (100 mg, 0.87 mmol) and potassium phosphate (1.2 g, 6 mmol) were added and the reaction mixture was stirred for 10 min. at RT. 3-(1-Bromoprop-1-en-2-yl)pyridine (0.772 g, 3.9 mmol) was added dropwise and the reaction mixture was purged with nitrogen. The reaction mixture was heated at 85° C. for 2 h and 140° C. for 5 h (prolonged heating in some cases was required). DMF was evaporated under reduced pressure, the residue was diluted with water and the solid was filtered. The solid material was purified by silica gel chromatography (100-200 mesh). Yield: 85 mg. 1HNMR (CD3OD, TFA salt) δ (ppm): 9.05 (d, 1H), 8.78 (d, 1H), 8.60 (d, 1H), 7.90 (m, 1H), 7.30 (d, 2H), 7.18 (d, 1H), 7.10 (d, 1H), 4.75 (m, 1H), 4.40 (m, 1H), 3.82 (m, 1H), 3.60 (m, 1H), 3.20 (m, 2H), 3.10 (s, 3H), 2.42 (s, 3H), 2.10 (s, 3H).

Workup

  1. customthe reaction mixture was purged with nitrogen
  2. temperatureThe reaction mixture was heated at 85° C. for 2 h and 140° C. for 5 h (
  3. temperatureprolonged heating in some cases
  4. customDMF was evaporated under reduced pressure
  5. additionthe residue was diluted with water
  6. filtrationthe solid was filtered
  7. customThe solid material was purified by silica gel chromatography (100-200 mesh)

Sources & evidence

ORD record
ord-c992f8af49df4147b054bec49211ea29
Source dataset
uspto-grants-2014_12
Patent number
US08907097B2

Reaction notes

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