Vol.:(0123456789) 1 3
Catal Lett
DOI 10.1007/s10562-017-2163-9
Pd/AlO(OH): A Heterogeneous, Stable and Recyclable Catalyst
for N-Arylation of Aniline Under Ligand-Free Aerobic Condition
Sundaram Ganesh Babu
1,2
· Balakumar Emayavaramban
1
· Peter Jerome
1
·
Ramasamy Karvembu
1
Received: 14 March 2017 / Accepted: 2 August 2017
© Springer Science+Business Media, LLC 2017
Graphical Abstract
Keywords Pd/AlO(OH) · Buchwald–Hartwig coupling ·
Ligand-free · Reusable · Heterogeneous · Aerobic condition
1 Introduction
Amines are ubiquitous in biology. Many neurotransmitters
are amines, including epinephrine, norepinephrine, dopa-
mine, serotonin and histamine. Many amine-based drugs are
designed to mimic or to interfere with the action of natural
amine neurotransmitters. Ephedrine and phenylephrine, as
amine hydrochlorides, are used as decongestants. Due to
their interesting physiological activities, secondary amines
are extremely important pharmacophores in numerous bio-
logically active compounds, which have greatly been touted
in drug discovery where the secondary amine can be utilized
as important scafolding for further manipulations [1]. Sec-
ondary amines are also a vital class of intermediates in the
preparation of natural products. With the growing repertoire
Abstract Many synthetic methods have been reported to
construct an aryl-nitrogen bond. But they mainly sufer from
the usage of expensive ligands. Herein, we report highly
efective, heterogeneous, reusable and ligand-free nanocata-
lyst for the Buchwald-Hartwig coupling reaction under aero-
bic condition. Wafer-like structure with nano-porous nature
of AlO(OH) was identifed with TEM and BET surface area
analyses. Zero valent Pd nanoparticles (with less than 10 nm
crystallite size which strongly evident from TEM analysis)
were observed in XRD pattern, which was further confrmed
by XPS studies. The reaction conditions were optimized and
the scope of the reaction was extended with various aryl
halides and aniline using low amount of Pd (0.31 mol%)
based heterogeneous catalyst. Heterogeneity, reusability and
stability (confrmed by XRD) were found to be reasonable.
Use of meagre amount of Pd and the ligand-free aerobic
condition make this system economically as well as envi-
ronmentally feasible.
* Sundaram Ganesh Babu
Sundaram.Babu@uct.ac.za
* Ramasamy Karvembu
kar@nitt.edu
1
Department of Chemistry, National Institute of Technology,
Tiruchirappalli 620015, India
2
Catalysis Institute, Department of Chemical Engineering,
University of Cape Town, Cape Town 7701, South Africa