Chloroform → 4-(3,4-dihydro-2H-pyrrol-5-yl)aniline

HRID 2236506Notes

Reaction equation

HRID 2236506 reaction equation
[Li+].C[Si]([N-:6][Si](C)(C)C)(C)C.C(Cl)(Cl)Cl.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[H+].[B-](F)(F)(F)F.Br[C:35]1[CH:40]=[CH:39][C:38]([C:41]2[CH2:42][CH2:43][CH2:44][N:45]=2)=[CH:37][CH:36]=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].C1(C)C=CC=CC=1>[N:45]1[CH2:44][CH2:43][CH2:42][C:41]=1[C:38]1[CH:39]=[CH:40][C:35]([NH2:6])=[CH:36][CH:37]=1

Participants

8

Reactant 5

HCID 6212ChloroformHCID 28118Tetrafluoroboric acidHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2733832Lithium HexamethyldisilazideHCID 114246115-(4-Bromophenyl)-3,4-dihydro-2h-pyrrole

Product 1

HCID 593001464-(3,4-dihydro-2H-pyrrol-5-yl)anilineYield 76.4%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

LiHMDS (1.67 g, 10.0 mmol) is added to a 100 mL round bottom flask. Toluene (25 mL) is added followed by addition of Pd2(dba)3.CHCl3 (100 mg, 0.1 mmol) and P(tBu)3.HBF4 (78 mg, 0.27 mmol). 5-(4-Bromo-phenyl)-3,4-dihydro-2H-pyrrole (1.5 g, 6.7 mmol) is added to the flask. After degassing, the mixture is stirred at room temperature overnight. TLC is used to determine complete consumption of the starting bromide. The reaction mixture is diluted with ether and poured into dilute HCl (aq). The ether layer is discarded and the aqueous layer is basified with NH4OH and extracted with CH2Cl2. The CH2Cl2 layer is dried and concentrated to provide the desired product (820 mg, 76%). 1H NMR (300 MHz, CDCl3) ∂ 7.66 (2H, d, J=8.4 Hz), 6.67 (2H, d, J=8.1 Hz), 3.98-4.03(2H, m), 3.88 (2H, br), 2.85-2.92 (2H, m), 1.97-2.04 (2H, m). MS (ESI): 162 (M+1)+1.

Workup

  1. customAfter degassing
  2. customconsumption of the starting bromide
  3. additionThe reaction mixture is diluted with ether
  4. additionpoured into dilute HCl (aq)
  5. extractionextracted with CH2Cl2
  6. dry with materialThe CH2Cl2 layer is dried
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-dafd16dfabef49be80f72a27b43cbe91
Source dataset
uspto-grants-2010_05
Patent number
US07713994B2

Reaction notes

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