Microwave-Assisted Copper-Catalyzed One-Pot Synthesis of 2-
Aryl/Heteroaryl-4-Quinolones via Sequential Intramolecular Aza-
Michael Addition and Oxidation
Priti Singh,
[a]
Santosh Kumar Sahoo
+
,
[a]
Nerella Sridhar Goud
+
,
[a, b]
Baijayantimala Swain,
[a]
Venkata Madhavi Yaddanapudi,
[a]
and Mohammed Arifuddin*
[a, c]
Abstract: A protocol has been developed that allows the
synthesis of 2-aryl/heteroaryl-4-quinolones from readily avail-
able, affordable starting materials. The reaction proceeds
under microwave conditions with moderate to high yields in
the presence of copper catalyst. Short reaction time, good
functional group tolerance, high atom economy, non-toxic
byproduct and no use of special ligands emphasize the
applicability of this method in organic synthesis.
Introduction
4-Quinolone and its derivatives are reckoned as privileged
chemotypes that are embedded in a wide range of biologically
and therapeutically active compounds.
[1]
Apart from pharma-
ceuticals, various natural products also exemplify the presence
of quinoline moiety in general and 4-quinolone scaffold in
particular.
[2]
4-Quinolone/Quinoline moiety is key in eliciting
diverse biological activity like anti-tubercular,
[3]
antimalarial,
[4]
antibacterial (ciprofloxacin, levofloxacin, moxifloxacin),
hypolipidemic,
[5]
antiviral,
[6]
xanthine oxidase inhibition,
[7]
and
antimitotic effect
[8]
(Figure 1). Last five decades have witnessed
widespread growth of 4-quinolone based antibiotics not only to
combat common clinical pathogens but also to tackle resistant
bacterial infection due to their potent, broad-spectrum, bacter-
icidal activity.
[9,10]
Although with time, novel modifications in 4-quinolone
scaffold have generated more potent antibacterial congeners to
uphold its status of go-to antibiotic, however, their synthesis
remains challenging that demands straightforward innovation
and efficient protocol.
Various synthetic protocols have been reported previously
for the formation of 2-substituted-4-quinolones.
[11]
Most com-
mon method of it involves condensation of anilines with β-keto
esters followed by cyclization of the formed β-arylaminoacry-
lates by classical approaches like Conrad-Limpach and Niemen-
towski reactions,
[12]
base-promoted cyclization of N-
(ketoaryl)amides (the Camps cyclization).
[13]
However, these
reactions require harsh conditions like high temperature, strong
acids that significantly limits its application.
Further strategies include non-traditional synthetic method
utilizing transition metals such as palladium-catalysed carbon-
ylation, titanium-mediated reductive coupling, and ruthenium-
catalysed reduction reactions. Poor yield, long reaction time,
pre-functionalization and harsh conditions used in these
reactions calls for further optimization of reaction conditions.
[a] P. Singh, S. Kumar Sahoo,
+
Dr. N. Sridhar Goud,
+
B. Swain,
Dr. V. Madhavi Yaddanapudi, Dr. M. Arifuddin
Department of Chemical Science,
National Institute of Pharmaceutical, Education, and Research (NIPER),
Balanagar, Hyderabad – 500037, Telengana State (India)
[b] Dr. N. Sridhar Goud
+
Present Address: Molecular Imaging Branch, NIMH, National Institutes of
Health (NIH), Bethesda – 20892 (USA)
[c] Dr. M. Arifuddin
Present Address: Synergy Community Welfare Research Center (SCWRC),
Head office, Panacea, Synergy India Foundaion, 4th Floor, TSWREIS
building,
Masab Tank Hyderabad – 500028 (India)
E-mail: arifabib@gmail.com
yvmadhavi.niperhyd@gov.in
[
+
] These authors contributed equally.
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/ajoc.202200181
Figure 1. Representative therapeutic agents containing quinoline/quinolone
moiety.
Research Article
doi.org/10.1002/ajoc.202200181
www.asianjoc.org
Asian J. Org. Chem. 2022, e202200181 (1 of 7) © 2022 Wiley-VCH GmbH