Mol Divers (2012) 16:113–119
DOI 10.1007/s11030-011-9334-1
FULL-LENGTH PAPER
Multicomponent synthesis of acylated short peptoids
with antifungal activity against plant pathogens
Matías D. Galetti · Adriana M. Cirigliano ·
Gabriela M. Cabrera · Javier A. Ramírez
Received: 13 April 2011 / Accepted: 30 August 2011 / Published online: 16 September 2011
© Springer Science+Business Media B.V. 2011
Abstract In this article, we describe the synthesis of a small
library of short peptoids composed of four glycine residues
and acylated with a fatty acid that showed a remarkable
in vitro activity against two fungal plant pathogens. Their
straightforward synthesis implied two consecutive Ugi reac-
tions and can be efficiently extended to the construction of
highly diverse libraries.
Keywords Acylated peptoids · Multicomponent reaction ·
Plant pathogen · Antifungal
Plants are constantly exposed to a variety of pathogenic
microorganisms present in their environments. Diseases
caused by pathogens, including bacteria, fungi, and viruses,
significantly contribute to the overall loss in crop yield world-
wide and constitute an emerging threat to the global food
security [1]. Many of the currently available antimicrobial
agents for agriculture are highly toxic and non-biodegrad-
able and cause extended environmental pollution [2].
Antimicrobial peptides (AMPs) (12–50 amino acids long),
known also as innate immunity host defense peptides or
innate defense regulators, are key components of the innate
immune system in all phyla, providing a fast-acting defense
against invading pathogens [3, 4]. A subfamily of AMPs with
strong antimicrobial activity includes lipopeptides, which
Electronic supplementary material The online version of this
article (doi:10.1007/s11030-011-9334-1) contains supplementary
material, which is available to authorized users.
M. D. Galetti · A. M. Cirigliano · G. M. Cabrera · J. A. Ramírez (B )
Departamento de Química Orgánica and UMYMFOR
(CONICET—Facultad de Ciencias Exactas y Naturales),
Universidad de Buenos Aires, Pabellón 2, Piso 3,
Ciudad Universitaria, C1428EGA, Buenos Aires, Argentina
e-mail: jar@qo.fcen.uba.ar
are produced non-ribosomally in bacteria and fungi. Lipo-
peptides consist of a short linear or cyclic peptide sequence
to which a fatty acid moiety is covalently attached at the
N terminus [5].
Recently, a new family of synthetic ultrashort lipopep-
tides (Fig. 1) composed of only four amino acid residues
conjugated to long-chain aliphatic acids has been reported.
These compounds have a broad spectrum of in vivo and in
vitro antimicrobial activity against human-pathogenic yeasts,
fungi, and bacteria [6], also affecting phytopathogenic fungi
and bacteria [7].
Peptoids are a class of oligomeric N-substituted glycines
that mimic the primary natural structure of peptides [8, 9].
They are attractive non-natural molecules for drug discovery
approaches because of their many biological activities and
proteolytic stability. Many peptoids have been shown to be
capable of acting as protein ligands with high affinity [10].
The most common method for the preparation of peptoids
is the solid-phase submonomer procedure [11]. This method
involves an iterative acylation reaction, with an R-haloacetyl
moiety that is common to all backbone elongation processes
and an iterative amination reaction using the commercially
available primary amines, and has been recently employed
to synthesize peptoid mimetics of antimicrobial lipopeptides
[12]. An alternative approach involves the use of the Ugi four-
component reaction (U-4CR) [13], which is a versatile tool
for the construction of peptoid and mixed peptoid–peptide
backbones. Repetitive or consecutive Ugi reactions have been
used in the synthesis of peptide nucleic acid oligomers and in
one-pot macrocyclizations [14, 15]. However, the assembly
of pure peptoid backbones in a consecutive fashion has not
been extensively explored [16, 17].
In this article, we describe the synthesis of a small library
of N-substituted tetraglycines acylated with a long-chain
alkyl residue. The structures resemble those of the antifungal
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