Triphenylphosphine → 9-Acetylamino-5-(2-methanesulfenylpyrimidin-4-yl)pyrido[3',2':4,5]pyrrolo[1,2-c]pyrimidine

HRID 2054355Notes

Reaction equation

HRID 2054355 reaction equation
[C:1]([NH:4][C:5]1[N:10]2[C:11]3[N:18]=[CH:17][CH:16]=[CH:15][C:12]=3[C:13](I)=[C:9]2[CH:8]=[CH:7][N:6]=1)(=[O:3])[CH3:2].[CH3:19][S:20][C:21]1[N:26]=[C:25]([Sn](C)(C)C)[CH:24]=[CH:23][N:22]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Li+].[Cl-]>O1CCOCC1.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].[Cu]I>[C:1]([NH:4][C:5]1[N:10]2[C:11]3[N:18]=[CH:17][CH:16]=[CH:15][C:12]=3[C:13]([C:23]3[CH:24]=[CH:25][N:26]=[C:21]([S:20][CH3:19])[N:22]=3)=[C:9]2[CH:8]=[CH:7][N:6]=1)(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 433294Lithium ChlorideHCID 111523439-Acetylamino-5-Iodopyrido[3',2':4,5]Pyrrolo[1,2-c]PyrimidineHCID 112662292-(Methylthio)-4-(trimethylstannyl)pyrimidine

Product 1

HCID 99682739-Acetylamino-5-(2-methanesulfenylpyrimidin-4-yl)pyrido[3',2':4,5]pyrrolo[1,2-c]pyrimidineYield 16.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 20a (130 mg, 0.37 mmol), 2-methanesulfenyl-4-trimethylstannylpyrimidine (93 mg, 1.10 mmol), Pd2(dba)3 (76 mg, 0.07 mmol), PPh3 (39 mg, 0.15 mmol), LiCl (47 mg, 1.10 mmol) and CuI (14 mg, 0.07 mmol) in dioxane (10 ml) was refluxed for 1.5 hours. The organic solvent was removed and the oil dissolved in CH2Cl2. The organic solution was extracted four times with 4N HCl and the aqueous solution basified with solid Na2CO3. The aqueous solution was extracted with CH2Cl2. The organic layer was evaporated and purified by flash column chromatography. Elution with CH2Cl2/MeOH (99/1) gave 9-Acetylamino-5-(2-methanesulfenylpyrimidin-4-yl)pyrido[3′,2′:4,5]pyrrolo[1,2-c]pyrimidine (21 mg, 16%) as a yellow solid and with CH2Cl2/MeOH (95/5) gave 21 (30 mg, 26%) as a yellow solid.

Workup

  1. customThe organic solvent was removed
  2. dissolutionthe oil dissolved in CH2Cl2
  3. extractionThe organic solution was extracted four times with 4N HCl
  4. extractionThe aqueous solution was extracted with CH2Cl2
  5. customThe organic layer was evaporated
  6. custompurified by flash column chromatography
  7. washElution with CH2Cl2/MeOH (99/1)

Sources & evidence

ORD record
ord-41b154386de7434eb6dedd2a7d7a4aec
Source dataset
uspto-grants-2008_02
Patent number
US07329666B2

Reaction notes

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