Cesium carbonate → HCID 59452985, compound

HRID 419341Notes

Reaction equation

HRID 419341 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([N+:10]([O-])=O)[CH:3]=1.[N:13]1([CH:19]2[CH2:24][CH2:23][NH:22][CH2:21][CH2:20]2)[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1.C(=O)([O-])[O-].[Cs+].[Cs+].C(P(C1C=CC=CC=1C1C=CC=CC=1)C(C)(C)C)(C)(C)C>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:13]1([CH:19]2[CH2:24][CH2:23][N:22]([C:2]3[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([CH:3]=3)[NH2:10])[CH2:21][CH2:20]2)[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 786071,4'-BipiperidineHCID 1185334-Bromo-2-nitroanisoleHCID 27342152-(Di-tert-butylphosphino)biphenyl

Product 1

HCID 59452985HCID 59452985, compoundYield 26.5%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To 4-bromo-2-nitroanisole (2.02 g, 8.72 mmol) and 1,4′-bipiperidine (3.49 g, 20.7 mmol) in dioxane (80 mL) was added sequentially, cesium carbonate (6.74 g, 20.7 mmol), palladium (II) acetate (0.196 g, 0.870 mmol) and di-tert-butylphosphino-biphenyl (0.527 g, 1.77 mmol). The reaction was heated at 100° C. for 24 hours, filtered through Celite®, concentrated and purified by flash chromatography. The residue was taken up in EtOAc (100 mL) and Pd on carbon was added in one portion. The mixture was stirred at rt under H2 (1 atm.) until complete by TLC. The reaction was filtered through Celite® and concentrated to provide the title compound of step A (0.667 g, 2.31 mmol, 26% over two steps). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.32-1.40 (m, 2H), 1.43-1.54 (m, 6H), 1.73 (d, J=12.1 Hz, 2H), 2.18-2.28 (m, 1H), 2.41-2.47 (m, 6H), 3.43 (d, J=12.5 Hz, 2H), 3.65 (s, 3H), 4.52 (s, 2H), 6.06 (dd, J=8.6, 2.7 Hz, 1H), 6.28 (d, J=2.9 Hz, 1H), 6.60 (d, J=8.8 Hz, 1H).

Workup

  1. filtrationfiltered through Celite®
  2. concentrationconcentrated
  3. custompurified by flash chromatography
  4. additionPd on carbon was added in one portion
  5. filtrationThe reaction was filtered through Celite®
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-9f8c9d7ed8924d1a9b4282f3fb9318c8
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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