1-Cyclohexenylboronic acid → 1-(3-Cyclohex-1-enyl-4-nitro-phenyl)-4-methyl-piperazine

HRID 2367765Notes

Reaction equation

HRID 2367765 reaction equation
Br[C:2]1[CH:3]=[C:4]([N:11]2[CH2:16][CH2:15][N:14]([CH3:17])[CH2:13][CH2:12]2)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].[C:18]1(B(O)O)[CH2:23][CH2:22][CH2:21][CH2:20][CH:19]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:18]1([C:2]2[CH:3]=[C:4]([N:11]3[CH2:16][CH2:15][N:14]([CH3:17])[CH2:13][CH2:12]3)[CH:5]=[CH:6][C:7]=2[N+:8]([O-:10])=[O:9])[CH2:23][CH2:22][CH2:21][CH2:20][CH:19]=1

Participants

4

Reactant 2

HCID 38629021-Cyclohexenylboronic acidHCID 117815411-(3-Bromo-4-nitrophenyl)-4-methylpiperazine

Product 1

HCID 591285801-(3-Cyclohex-1-enyl-4-nitro-phenyl)-4-methyl-piperazineYield 123%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
100 °C

Procedure

A mixture of 102 mg (0.340 mmol) 1-(3-bromo-4-nitro-phenyl)-4-methyl-piperazine (as prepared in Example 9, step (a)), 59.7 mg (0.474 mmol) cyclohexen-1-ylboronic acid, 43.8 mg (0.0379 mmol) of tetrakis(triphenylphosphine)palladium (0) under Ar was treated with 206 μL (0.412 mmol) of 2.0 M degassed aq Na2CO3, 0.6 mL degassed anh toluene and 0.2 mL degassed anh EtOH and the mixture was heated at 100° C. for 21 h. After cooling to RT, the mixture was poured into EtOAc (10 mL), washed with brine (10 mL), dried (Na2SO4) and concentrated in vacuo. Chromatography on a 5-g silica SPE column with 1-3% EtOH in dichloromethane afforded 126 mg of the title compound (74% purity by RP-HPLC (C18 column) as a mixture with triphenylphosphine) as a yellow oil that was used in the following reaction without further purification. Mass spectrum (ESI, m/z): Calcd. for C17H23N3O3, 302.2 (M+H). found 302.2.

Workup

  1. additionwas treated with 206 μL (0.412 mmol) of 2.0 M
  2. customdegassed aq Na2CO3, 0.6 mL
  3. customdegassed anh toluene and 0.2 mL
  4. customdegassed anh EtOH
  5. temperatureAfter cooling to RT
  6. additionthe mixture was poured into EtOAc (10 mL)
  7. washwashed with brine (10 mL)
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9ef0e48556a04849acf57c16ba2ea1a9
Source dataset
uspto-grants-2014_04
Patent number
US08697716B2

Reaction notes

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