Cesium carbonate → 4-Chloro-9H-dipyrido[2,3-b;4',3'-d]pyrrole

HRID 60259Notes

Reaction equation

HRID 60259 reaction equation
[Cl:1][C:2]1[C:10]2[C:9]3[CH:11]=[C:12](C#N)[N:13]=[CH:14][C:8]=3[N:7](COCC[Si](C)(C)C)[C:6]=2[N:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.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]>[Cl:1][C:2]1[C:10]2[C:9]3[CH:11]=[CH:12][N:13]=[CH:14][C:8]=3[NH:7][C:6]=2[N:5]=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 582666684-Chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile

Product 1

HCID 583650494-Chloro-9H-dipyrido[2,3-b;4',3'-d]pyrrole

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 4-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (1 eq.), the appropriate amine (5 eq.), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.2 eq), tris(dibenzylideneacetone)dipalladium(0) (0.1 eq.), and cesium carbonate (2 eq.) in 1,4-dioxane was heated between 100° C. to 110° C. until the reaction deemed complete. The reaction mixture was cooled then diluted with water and extracted with an appropriate solvent. The resultant residue was purified by flash chromatography on silica using either an ethyl acetate in heptane or methanol in dichoromethane gradient. The purified material was then deprotected using the conditions described below.

Workup

  1. temperatureThe reaction mixture was cooled
  2. extractionextracted with an appropriate solvent
  3. customThe resultant residue was purified by flash chromatography on silica using

Sources & evidence

ORD record
ord-32b0828cdaac467486c02ed82bfd9093
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Reaction notes

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