Cesium carbonate → 1-Tert-butyl 4-ethyl 4-(2-cyclopropylallyl)piperidine-1,4-dicarboxylate

HRID 1848496Notes

Reaction equation

HRID 1848496 reaction equation
Br[C:2](=[CH2:22])[CH2:3][C:4]1([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:9][CH2:8][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:6][CH2:5]1.[CH:23]1([B-](F)(F)F)[CH2:25][CH2:24]1.[K+].C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.CCOC(C)=O.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH:23]1([C:2](=[CH2:22])[CH2:3][C:4]2([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:9][CH2:8][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:6][CH2:5]2)[CH2:25][CH2:24]1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 23697338Potassium cyclopropyltrifluoroborateHCID 867095021-Tert-butyl 4-ethyl 4-(2-bromoallyl)piperidine-1,4-dicarboxylate

Product 1

HCID 867095071-Tert-butyl 4-ethyl 4-(2-cyclopropylallyl)piperidine-1,4-dicarboxylate

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

1-tert-butyl 4-ethyl 4-(2-bromoallyl)piperidine-1,4-dicarboxylate (1.0 g, 2.66 mmol), potassium cyclopropyltrifluoroborate (0.413 g, 2.79 mmol), cesium carbonate (2.60 g, 7.97 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.058 g, 0.080 mmol) were taken up in toluene (14 mL) and water (1.39 mL) in a microwave vial, degassed and heated at 80° C. overnight. The reaction mixture was cooled and LC/MS was taken which showed almost completion of reaction. The reaction mixture was diluted with EtOAc and water. Aqueous layer was extracted with EtOAc (2×), the combined organic layers were dried over anhydrous MgSO4, filtered, concentrated, and purified by silica gel column chromatography (RediSep Gold, 80 g) using (0-30) % EtOAc/Hexanes as mobile phase to afford the title compound.

Workup

  1. customwater (1.39 mL) in a microwave vial, degassed
  2. temperatureThe reaction mixture was cooled
  3. customcompletion of reaction
  4. extractionAqueous layer was extracted with EtOAc (2×)
  5. dry with materialthe combined organic layers were dried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by silica gel column chromatography (RediSep Gold, 80 g)

Sources & evidence

ORD record
ord-9fce99df9bd04d65a0b65ae853c25e16
Source dataset
uspto-grants-2015_02
Patent number
US08952166B2

Reaction notes

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