Synlett 2016; 27(08): 1227-1231
DOI: 10.1055/s-0035-1561113
cluster
© Georg Thieme Verlag Stuttgart · New York

Palladium–Polypyrrole Nanocomposites Pd@PPy for Direct C–H Functionalization of Pyrroles and Imidazoles with Bromoarenes

Pierre Bizouard
a  Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 6302, Université de Bourgogne Franche-Comté, 9 Avenue Alain Savary, 21078 Dijon Cedex, France   Email: julien.roger@u-bourgogne.fr   Email: jean-cyrille.hierso@u-bourgogne.fr
,
Christelle Testa
a  Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 6302, Université de Bourgogne Franche-Comté, 9 Avenue Alain Savary, 21078 Dijon Cedex, France   Email: julien.roger@u-bourgogne.fr   Email: jean-cyrille.hierso@u-bourgogne.fr
,
Veronika A. Zinovyeva*
b  Institut de Physique Nucléaire, CNRS-IN2P3, Univ. Paris-Sud, Université Paris-Saclay, 91406 Orsay Cedex, France   Email: veronika.zinovyeva@u-psud.fr
,
Julien Roger*
a  Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 6302, Université de Bourgogne Franche-Comté, 9 Avenue Alain Savary, 21078 Dijon Cedex, France   Email: julien.roger@u-bourgogne.fr   Email: jean-cyrille.hierso@u-bourgogne.fr
,
Jean-Cyrille Hierso*
a  Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 6302, Université de Bourgogne Franche-Comté, 9 Avenue Alain Savary, 21078 Dijon Cedex, France   Email: julien.roger@u-bourgogne.fr   Email: jean-cyrille.hierso@u-bourgogne.fr
c  Institut Universitaire de France (IUF), 103 Boulevard Saint Michel, 75005 Paris Cedex, France
› Author Affiliations
Further Information

Publication History

Received: 10 November 2015

Accepted after revision: 14 December 2015

Publication Date:
05 January 2016 (online)


Dedicated to the memory of Dr. Guy Lavigne

Abstract

Palladium–polypyrrole nanocomposites (Pd@PPy) with unique combination of high palladium dispersion (nanoparticle size 2.4 nm) and high palladium content (35 wt%) are efficient catalysts for the selective arylation of substituted pyrroles and imidazoles with either activated or deactivated aryl bromides. The performances of the recoverable supported palladium catalyst matches the best performances of homogeneous systems based on Pd(OAc)2 at 0.5–0.2 mol%, and largely overwhelm the classical Pd/C catalyst.

Supporting Information

 
  • References and Notes

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  • 14 Typical Procedure All reactions were run under argon in Schlenk tubes using vacuum lines. DMAc analytical grade was not distilled before use. KOAc (99%) was used. Commercial aryl bromides, pyrroles, and imidazoles were used without purification. The reactions were followed by GC and NMR spectroscopy. 1H NMR spectra were recorded with a Bruker 300 MHz spectrometer in CDCl3 solutions. Chemical shifts are reported in ppm relative to CDCl3 (7.25 for 1H NMR). Flash chromatography was performed on silica gel (230–400 mesh). In a typical procedure, the aryl bromide (1 mmol), pyrrole (2 mmol), and KOAc (2 mmol) were introduced in a Schlenk tube, equipped with a magnetic stirring bar. The catalyst [either Pd@PPy,5 or Pd(OAc)2 at 0.02–2.0 mol%] and DMAc (2.5 ml) were added, and the Schlenk tube was purged several times using vacuum/argon flow. The Schlenk tube was placed in a preheated oil bath at 150 °C, and reactants were allowed to stir for 17 h. The reaction mixture was analyzed by GC and NMR to determine the conversion of aryl bromide. The solvent was then removed by heating the reaction vessel under vacuum, and the residue formed was charged directly onto a silica gel column. The products were eluted, using an appropriate ratio of EtOAc and heptane. Recycling procedure were based on simple Pd@PPy powder paper filtration, rinsing with a small portion of organic solvent, and drying under vacuum at 60 °C for 4 h. Subsequent catalytic tests were conducted using DMAc at 150 °C in the presence of KOAc and sufficient Pd@PPy collected from several experiments.
  • 15 1-[4-(5-Acetyl-1-methyl-1H-pyrrol-2-yl)phenyl]ethanone (6a) The reaction of 4-bromoacetophenone (0.100 g, 1 mmol), 1-methyl-2-acetylpyrrole (0.120 mL, 2 mmol), and KOAc (0.098 g, 2 mmol) with Pd@PPy (0.003 g, 2% mol) affords the corresponding product 6a in 28% isolated yield. 1H NMR (200 MHz, CDCl3): δ = 8.02 (d, J = 8.4 Hz, 2 H), 7.51 (d, J = 8.4 Hz, 2 H), 7.03 (d, J = 4.0 Hz, 1 H), 6.29 (d, J = 4.0 Hz, 1 H), 3.91 (s, 3 H), 2.64 (s, 3 H), 2.48 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 197.4, 188.7, 141.4, 136.4, 136.3, 132.7, 129.3, 128.6, 119.7, 110.1, 35.4, 27.5, 26.7. Anal. Calcd (%) for C15H15NO2: C, 74.67; H, 6.27; 5.81. Found: C, 73.92; H, 6.33; N, 5.40. HRMS (ESI+): m/z [M + H+] calcd for C15H15NO2: 242.118; Found: 242.172.
  • 16 1-Methyl-5-(m-tolyl)-1H-pyrrole-2-carbaldehyde (7d) The reaction of 3-bromotoluene (0.060 mL, 1 mmol), 1-methyl-2-formylpyrrole (0.100 ml, 2 mmol), and KOAc (0.098 g, 2 mmol) with Pd@PPy (0.003 g, 2 mol%) affords the corresponding product 7d in 41% isolated yield. 1H NMR (300 MHz, CDCl3): δ = 9.57 (s, 1 H), 7.37–7.32 (m, 1 H), 7.26–7.20 (m, 3 H), 6.96 (dd, J = 4.1 Hz, 1 H), 6.29 (d, J = 4.1 Hz, 1 H), 3.93 (s, 3 H), 2.41 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 179.5, 144.6, 138.4, 133.0, 131.1, 129.9, 129.4, 128.5, 126.3, 124.5, 110.7, 34.4, 21.5. Anal. Calcd (%) for C13H13NO: C, 78.36; H, 6.58; N, 7.03. Found: C, 77.93; H, 6.53; N, 6.70. HRMS (ESI+): m/z [M + H+] calcd for C13H13NO: 200.107; found: 200.190.