Cesium carbonate → (S)-(2,4-Dichlorobenzyl)-[1-(5-nitropyridin-2-yl)-pyrrolidin-3-yl]-amine

HRID 252101Notes

Reaction equation

HRID 252101 reaction equation
[Cl:1][C:2]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:3]=1[CH2:4][NH:5][C@H:6]1[CH2:10][CH2:9][NH:8][CH2:7]1.Br[C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][N:18]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:3]=1[CH2:4][NH:5][C@H:6]1[CH2:10][CH2:9][N:8]([C:17]2[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][N:18]=2)[CH2:7]1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 782402-Bromo-5-nitropyridineHCID 66569981(S)-N-(2,4-Dichlorobenzyl)pyrrolidin-3-amine

Product 1

HCID 59860353(S)-(2,4-Dichlorobenzyl)-[1-(5-nitropyridin-2-yl)-pyrrolidin-3-yl]-amineYield 92%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

Degas a mixture of (S)-(2,4-dichlorobenzyl)-pyrrolidin-3-ylamine (245 mg, 1 mmol), 2-bromo-5-nitropyridine (168 mg, 0.83 mmol) and cesium carbonate (404 g, 1.24 mmol) in dry toluene (2 mL) by bubbling nitrogen for 15 min. Add tris(dibenzylideneacetone)dipalladium (0) (15 mg, 0.016 mmol) and (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (18 mg, 0.024 mmol). Stir the resulting mixture at 90° C. overnight. Chromatograph on silica gel and concentrate to give the title compound (280 mg, 92%).

Workup

  1. customDegas
  2. customby bubbling nitrogen for 15 min
  3. concentrationChromatograph on silica gel and concentrate

Sources & evidence

ORD record
ord-340af69265cd43a3be5ccb593dc32d01
Source dataset
uspto-grants-2011_01
Patent number
US07868014B2

Reaction notes

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