PAOLA PELUSO - icb.cnr.it · PAOLA PELUSO . CNR Researcher . Istituto di Chimica Biomolecolare ICB - CNR . Date and Place of birth . June 20, 1965; Lecce, Italy . Nationality Italian
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PAOLA PELUSO CNR Researcher Istituto di Chimica Biomolecolare ICB - CNR Date and Place of birth June 20, 1965; Lecce, Italy Nationality Italian Email p.peluso@icb.cnr.it ______________________________________________________________________________
Curriculum Vitae MAIN RESEARCH INTERESTS New Materials
• Design and applications of metal organic frameworks
• Applications of polysaccharide-based polymers for molecular recognition
Chiral Chromatography and Molecular Recognition
• HPLC enantioseparations, method development, multimodal elution conditions
• Recognition mechanisms on polysaccharide-based chiral stationary phases
• Enantioseparation of atropisomeric compounds
• Design and preparation of new chiral stationary phases
Organic Chemistry
• Chirality
• Stereochemistry
• Molecular recognition
Organic Synthesis
• Bridged polycyclic compounds
• Heterocyclic chemistry
• Sulfone chemistry
CURRENT RESEARCH (2009-2017) Synthesis and applications of 4,4’-bipyridine-based metal-organic frameworks (MOFs)
• Aubert, E.; Abboud, M.; Doudouh, A.; Durand, P.; Peluso, P.; Ligresti, A.; Vigolo, B.; Cossu, S.; Pale,
P.; Mamane, V.
Silver(I) coordination polymers with 3,3’,5,5’-tetrasubstituted 4,4’-bipyridine ligands: towards new
porous chiral materials.
RCS Advances 2017, 7, 7358-7367.
• Aubert, E.; Doudouh, A.; Peluso, P.; Mamane, V.
Ordered water and bipyridine channels in a {[Cu(SiF6)(C10N2H8)2]·(C10N2H8)2·(H2O)5}n porous
coordination polymer.
Acta Crystallogr. E 2016, E72, 1654-1658.
• Peluso, P.; Mamane, V.; Cossu, S. Homochiral metal-organic frameworks and their application in chromatography enantioseparations.
J. Chromatogr. A 2014, 1363, 11-26 (invited review on Special Issue Enantioseparation 2014).
2
Halogen bond-driven enantioseparations • Peluso, P.; Mamane, V.; Aubert, E.; Dessì, A.; Dallocchio, R.; Dore, A.; Pale, P.; Cossu, S.
Insights into halogen bond-driven enantioseparations.
J. Chromatogr. A 2016, 1467, 228-238 (invited article on Special Issue Enantioseparation 2016).
• Peluso, P.; Mamane, V.; Cossu, S.
LC Enantioseparations of halogenated compounds on polysaccharide-based chiral stationary
phases: role of halogen substituents in molecular recognition.
Chirality 2015, 27, 667-684 (invited article on Special Issue Chirality in Separation Science and
Molecular Recognition).
• Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
Insights into the impact of shape and electronic properties on the enantioseparation of
polyhalogenated 4,4’-bipyridines on polysaccharide-type selectors. Evidence of stereoselective
halogen bonding interactions.
J. Chromatogr. A 2014, 1345, 182-192.
Synthesis and enantioseparation of atropisomeric 4,4’-bipyridines • Mamane, V.; Peluso, P.; Aubert, E.; Cossu, S.; Pale, P.
Chiral hexahalogenated 4,4’-bipyridines.
J. Org. Chem. 2016, 81, 4576-4587.
• Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
High-performance liquid chromatography enantioseparation of polyhalogenated 4,4’-bipyridines on
polysaccharide-based chiral stationary phases under multimodal elution.
J. Sep. Sci. 2014, 37, 2481-2489.
• Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
Optimization of the HPLC enantioseparation of 3,3’-dibromo-5,5’-disubstituted-4,4’-bipyridines using
immobilized polysaccharide-based chiral stationary phases.
J. Sep. Sci. 2013, 36, 2993-3003.
• Mamane, V.; Aubert, E.; Peluso, P.; Cossu, S.
Lithiation of prochiral 2,2’-dichloro-5,5’-dibromo-4,4’-bipyridine as a tool for the synthesis of chiral
polyhalogenated 4,4’-bipyridines.
J. Org. Chem. 2013, 78, 7683-7689.
• Mamane, V.; Aubert, E.; Peluso, P.; Cossu, S.
Synthesis, resolution, and absolute configuration of chiral 4,4′-bipyridines.
J. Org. Chem. 2012, 77, 2579-2583.
• Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
High performance liquid chromatography enantioseparation of atropisomeric 4,4’-bipyridines on
polysaccharide-type chiral stationary phases: impact of substituents and electronic properties.
J. Chromatogr. A 2012, 1251, 91-100.
Enantioseparations and molecular recognition mechanisms on polysaccharide-based CSPs • Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
Recent trends and applications in liquid phase chromatography enantioseparation of atropisomers.
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Electrophoresis 2017, 38, doi:10.1002/elps.201600502 (invited review on Special Issue Liquid Phase
Enantioseparations).
• Peluso, P.; Cossu, S.
Comparative HPLC enantioseparation of thirty six aromatic compounds on four columns of the Lux
series. Impact of substituents, shapes and electronic properties.
Chirality 2013, 25, 709-718.
• Peluso, P.; Fabbri, D.; Dettori, M. A.; Delogu, G.; Zambrano, V.; Cossu, S.
High-performance liquid chromatographic enantioseparation of atropisomeric biphenyls on seven
chiral stationary phases.
Curr. Org. Chem. 2011, 15, 1208-1229.
• Peluso, P.; Cossu, S.; Moretto, F.; Marchetti, M.
High performance liquid chromatographic enantioseparation of chiral bridged polycyclic compounds
on Chiralcel OD-H and Chiralpak OT(+).
Chirality 2009, 21, 507-518.
LANGUAGES • Italian
• English
EDUCATION 2003 PhD Degree in Chemical Sciences, Università Ca’ Foscari di Venezia in the group of Prof.
O. De Lucchi. Subject: Desymmetrization reactions of polycyclic alkenes.
1993 Laurea (MS Degree) in Chemistry, Università degli Studi di Pisa in the group of Prof. Rita
Menicagli. Subject: Synthesis and applications of new chiral stationary phases based on
1,3,5-triazine derivatives.
CAREER 2014-to date CNR Researcher, Istituto di Chimica Biomolecolare.
2009-2015 Member of the Internal Advisory Board, Istituto di Chimica Biomolecolare.
2008-2013 CNR Technologist, Istituto di Chimica Biomolecolare.
2001-2002 Research fellowship, Università Ca’ Foscari di Venezia. Subject: Desymmetrization
reactions of polycyclic alkenes.
1999-2000 Research fellowship, VIS Farmaceutici, Padova. Subject: Synthesis of biologically active
compounds.
1997-1998 Research fellowship, F.I.S. - Fabbrica Italiana Sintetici S.p.A., Vicenza. Subject: Synthesis of
pharmacologically active heterocyclic compounds.
1996 Research fellowship, CIBA-GEIGY S.p.A. Divisione Additivi, Bologna. Subject: Reactions of
hydrosilylation and oligomerization of organosilicon compounds.
1994-1995 CNR fellowship, Università degli Studi di Pisa. Subject: Carbonylation reactions of olefinic
substrates.
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Reviewer for the following international journals: Current Pharmaceutical Analysis, Current Analytical
Chemistry (Bentham Science Publishers); Chirality (Wiley), Journal of Chromatography A, Analytica Chimica
Acta (Elsevier); Analyst, Analytical Methods, New Journal of Chemistry (Royal Society of Chemistry); Journal
of the American Chemical Society (American Chemical Society); Materials (MDPI); Journal of Liquid
Chromatography and Related Techniques (Taylor & Francis).
COLLABORATIONS
• Università Ca’ Foscari di Venezia, Dipartimento di Scienze Molecolari e Nanosistemi.
Prof. Sergio Cossu
• Institut de Chimie de Strasbourg, UMR CNRS 7177, Equipe LASYROC.
Dr. Victor Mamane
• Université de Lorraine, UMR CNRS 7036.
Dr. Emmanuel Aubert
• Istituto di Metodologie Chimiche IMC – CNR
Dr.ssa Zeineb Aturki
INVITED CONFERENCES
• Université de Strasbourg (Faculté de Chimie), 2015.
High-performance liquid chromatography (HPLC) on polysaccharide-based chiral stationary phases.
Exploiting the size and shape of molecules to understand chiral recognition mechanisms.
• Istituto di Chimica Biomolecolare, Pozzuoli (NA) (ICB Seminar series 2015), CNR, 2015.
Cromatografia liquida ad alte prestazioni (HPLC) su fasi stazionarie chirali a base polisaccaridica:
enantioseparazioni, meccanismi di riconoscimento e high-throughput screening molecolare.
• Sassari Research Area, Seminar series 2009-2010, 2010. Molecular recognition in organic chemistry.
INTERNATIONAL CONGRESSES 2016
P. Spanu, A. De Mico, A. Cottarelli, F. Morelli, M. Zonfrillo, F. Ulgheri, P. Peluso, A. Mannu, F. Deligia, M.
Marchetti, G. Roviello, A. Reyes Romero, A. Doemling, M. P. Fuggetta, Synthesis and enantiomeric
separation of a novel spiroketal derivative: a potent human telomerase inhibitor with high in vitro anticancer
activity, XXIV EFMC International Symposium on Medicinal Chemistry. Manchester (UK), August 28 -
September 1, 2016.
2014
P. Peluso, V. Mamane, E. Aubert, S. Cossu, Exploiting halogen bonding interaction in high-performance
liquid chromatography enantioseparations, Chirality 2014. Praga (CZ), July 27-30, 2014.
5
2012 P. Peluso, V. Mamane, E. Aubert, S. Cossu, High-performance liquid chromatography enantioseparation of
atropisomeric 4,4’-bipyridines on immobilized polysaccharide-based Chiralpak IA and Chiralpak IC: impact of
substituents and electronic properties, 4th EuCheMS Chemistry Congress. Praga (CZ), August 26-30, 2012.
V. Mamane, E. Aubert, P. Peluso, S. Cossu, Atropisomeric chiral 4,4’-bipyridines, 4th EuCheMS Chemistry
Congress. Praga (CZ), August 26-30, 2012.
2010 P. Peluso, D. Fabbri, M. A. Dettori, G. Delogu, S. Cossu, HPLC Enantioseparation of structurally related
chiral compounds on seven chiral stationary phases and computational analysis of the analyte structures,
Ischia Advanced School of Organic Chemistry IASOC 2010. Ischia (Na), September 25-29, 2010.
2001
G. Borsato, S. Cossu, O. De Lucchi, F. Fabris, P. Peluso, Cyclotrimerisation of polycyclic olefins: an
asymmetric approach to a symmetric molecule, 2nd Italian-Japanese Symposium of Organic Chemistry
(JISOC-2). Kyoto, Japan, November 28-30, 2001.
1998
S. Cossu, O. De Lucchi, P. Peluso, R. Volpicelli, Enantiotopic discrimination in the reaction of chiral
alcoholates with Cs-symmetric bis(phenylsulfonyl)alkenes, 2nd Italian-Spanish Symposium on Organic
Chemistry (ISSOC-2). Lecce, June 7-11, 1998.
1996 G. Uccello-Barretta, A. Iuliano, R. Menicagli, P. Peluso, E. Pieroni, P. Salvadori, 1,3,5-Triazine multiselectors
systems: a new tool for chiral discriminations, 8th International Symposium on Chiral Discrimination.
Edimburgh Scotland, June 30 - July 3, 1996. CNR GRANTS 2015 Short term mobility program (three weeks), Équipe LASYROC, CNRS, Université de
Strasbourg.
2010 Annual assignment (€ 1950,00) for training programmes and professional updates.
PARTICIPATION IN RESEARCH PROJECTS 2012-2015 Title: 3rd generation bio-refinery integrated in the territory (BIT3G), MIUR.
Role: Participating researcher.
2010-2012 Title: Diversità molecolare nella sintesi chimica di composti biologicamente attivi di
rilevanza sociale, Regione Sardegna.
Role: Participating researcher.
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2008-to date Title: Chiral liquid chromatography, ADIR-Dipartimento di Scienze Molecolari e
Nanosistemi, Università Ca' Foscari di Venezia.
Role: Participating researcher.
2000 Title: New syntheses of pharmacologically active 1,2-pyridazines, MIUR.
Role: Project coordinator
PARTICIPATION IN TEACHING PROGRAMS Years: 2009-to date
Project: “Alternanza Scuola/Lavoro”
Role: Teacher and laboratory training coordinator
Subject: Molecular recognition and chiral chromatography
High-performance liquid chromatography
Partners: Liceo Scientifico Statale “G. Marconi”, Sassari (2009-to date)
Liceo Classico Statale “D.A. Azuni”, Sassari (2016)
Year: 2009
Project: XIX Settimana della Cultura Scientifica e Tecnologica, Ministero dell’Istruzione,
dell’Università e della Ricerca (March 23th-29th).
Role: Teacher and laboratory training coordinator
Subject: Analysis of organic molecules by means of gas chromatography and GC-mass
spectrometry.
Partner: Liceo Scientifico Statale “G. Marconi”, Sassari
Istituto Tecnico Industriale “G.M. Angioy”, Sassari.
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PUBLICATIONS 36 articles and reviews in international journals (11 as corresponding author), h-index: 11. Total numbers of citations: 318 [Source: Google Scholar, February 2017]
2017
36. Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
Recent trends and applications in liquid phase chromatography enantioseparation of atropisomers.
Electrophoresis 2017, 38, doi:10.1002/elps.201600502 (invited review on Special Issue Liquid Phase
Enantioseparations).
The term Atropisomerism defines a type of enantiomerism that
arises from hindered rotation around an axis that makes two
rotational isomers enantiomers. Atropisomeric compounds are
present in nature, being important building blocks of many
biologically active compounds. Atropisomers have been
extensively studied in environmental and toxicological chemistry
and, in particular, separating them has become a need in specific
fields as organic synthesis and pharmaceutical research. High-
performance liquid chromatography has been fruitfully applied in this context, and, despite HPLC separation
on chiral stationary phase (CSP) is considered as mature technology nowadays, in the last years several
advancements and applications contributed to study compounds where axial chirality is of utmost
importance. Moreover, dynamic chromatography has been exploited as a versatile tool for kinetic studies of
systems with slow internal motion gaining essential information on their stereodynamic behaviour. On this
basis, current topics and trends in liquid phase chromatography enantioseparation of atropisomers are
presented herein with specific focus on new representative applications with HPLC, covering years 2010-
2016. Some examples concerning supercritical fluid chromatography (SFC) applications are also reported.
This review aims to provide the reader with a modern overview of the field in order to highlight the renewed
interest towards the chemistry of molecules with atropisomeric properties. A systematic compilation of all
published literature has not been attempted.
35. Aubert, E.; Abboud, M.; Doudouh, A.; Durand, P.; Peluso, P.; Ligresti, A.; Vigolo, B.; Cossu, S.; Pale, P.;
Mamane, V.
Silver(I) coordination polymers with 3,3’,5,5’-tetrasubstituted 4,4’-bipyridine ligands: towards new porous
chiral materials.
RCS Advances 2017, 7, 7358-7367.
Coordination polymers (CP) assembled from 3,3’,5,5’-
tetrasubstituted 4,4’-bipyridines and silver salts have been
prepared and characterized by X-ray diffraction. Silver-
CPs based on infinite Ag-bipyridine chains were obtained
where one or two halogen atoms strongly interacted with
Ag. A homochiral MOF was also prepared using the
8
enantiopure 3,3′-dibromo-5,5′-bis(4-methoxyphenyl)-4,4′-bipyridine as ligand, while its racemic form only
formed a compact CP. Preliminary applications showed that the homochiral network is able to recognize the
enantiomers of rac-stilbene oxide and to control the cytotoxicity level of the Ag-based MOF toward a cell line
derived from adult human skin (HaCaT).
2016
34. Aubert, E.; Doudouh, A.; Peluso, P.; Mamane, V.
Ordered water and bipyridine channels in a {[Cu(SiF6)(C10N2H8)2]·(C10N2H8)2·(H2O)5}n porous coordination
polymer.
Acta Crystallogr. E 2016, E72, 1654-1658.
Water and 4,4'-bipyridine molecules can be accomodated inside the
channels of the porous coordination polymer [Cu(SiF6)(C10N2H8)2]n. Due
to the presence of these ordered species, the framework changes its
symmetry from P4/mmm reported in the literature to P21/c. These guests
4,4'-bipyridine forms chains where the molecules are bound by π··· π
stacking, filling pore of 6.5Å × 6.9 Å free aperture parallel to [100].
Ordered water molecules form infinite chain inside a second pore system
(1.6 Å × 5.3 Å free aperture) which is perpendicular to the first one.
33. Fuggetta, M. P.; De Mico, A.; Cottarelli, A.; Morelli, F.; Zonfrillo, M.; Ulgheri, F.; Peluso, P.; Mannu, A.;
Deligia, F.; Marchetti, M.; Roviello, G. N.; Reyes Romero, A.; Dömling, A.; Spanu, P.
Synthesis and enantiomeric separation of a novel spiroketal derivative: a potent human telomerase inhibitor
with high in vitro anticancer activity.
J. Med. Chem. 2016, 59, 9140-9149.
The synthesis, the enantiomeric separation and the characterization of new simple
spiroketal derivatives has been performed. The synthesised compounds have shown a
very high anticancer activity. Cell proliferation assay showed that they induce a
remarkable inhibition of cell proliferation in all cell lines treated, depending on culture
time and concentration. The compounds have also shown a potent nanomolar human Telomerase inhibition
activity and apoptosis induction. CD melting experiments demonstrate that spiroketal does not affect the G-
quadruplex (G4) thermal stability. Docking studies showed that telomerase inhibition could be determined by
a spiroketal interaction with the telomerase enzyme.
32. Peluso, P.; Mamane, V.; Aubert, E.; Dessì, A.; Dallocchio, R.; Dore, A.; Pale, P.; Cossu, S.
Insights into halogen bond-driven enantioseparations.
J. Chromatogr. A 2016, 1467, 228-238 (invited article on Special Issue Enantioseparation 2016).
9
Although the halogen bond (XB) has been so far mainly studied in
silico and in the solid state, its potential impact in solution is yet to
be fully understood. In this study, we describe the first systematic
investigation on the halogen bond in solvated environment by high-
performance liquid chromatography (HPLC). Thirty three
atropisomeric polyhalogenated-4,4’-bipyridines (HBipys), containing
Cl, Br and I as substituents, were selected and used as potential XB donors (XBDs) on two cellulose-based
chiral stationary phases (CSPs) containing potential XB acceptors (XBAs). The impact of the halogens on
the enantiodiscrimination mechanism was investigated and iodine showed a pivotal role on the
enantioseparation in non-polar medium. Electrostatic potentials (EPs) were computed to understand the
electrostatic component of CSP-analyte interaction. Moreover, van’t Hoff studies for ten HBipys were
performed and the thermodynamic parameters governing the halogen-dependent enantioseparations are
discussed. Finally, a molecular dynamic (MD) simulation is proposed to model halogen bond in
polysaccharide-analyte complexes by inclusion of a charged extra point to represent the positive ‘σ-hole’ on
the halogen atom. On the basis of both experimental results and theoretical data, we have profiled the
halogen bond as a chemo-, regio-, site- and stereoselective interaction which can work in HPLC environment
besides other known interactions based on the complementarity between selector and selectand.
31. Mamane, V.; Peluso, P.; Aubert, E.; Cossu, S.; Pale, P.
Chiral hexahalogenated 4,4’-bipyridines.
J. Org. Chem. 2016, 81, 4576-4587.
The preparation of 27 isomers of chiral
hexahalogeno-4,4’-bipyridines by means of two
complementary methods is described. The first
one is convergent and based on the LDA-induced 4,4’-dimerization of trihalopyridines, whereas the second
method is divergent and achieved through regioselective halogenation reactions of 4,4’-bipyridine-2,2’-
diones. Iodine in 2,2’-positions of the 4,4’-bipyridines was introduced by a copper-catalyzed Filkenstein
reaction (Buchwald procedure) performed on 2,2’-dibromo derivatives. Selected compounds of this new
family of atropisomeric 4,4’-bipyridines were enantioseparated by chiral High Performance Liquid
Chromatography (HPLC) and the absolute configurations of the separated enantiomers were assigned by
using X-ray diffraction (XRD) analysis. The later revealed that various halogen bond type are responsible for
crystal cohesion.
2015
30. Peluso, P.; Mamane, V.; Cossu, S.
LC Enantioseparations of halogenated compounds on polysaccharide-based chiral stationary phases: role of
halogen substituents in molecular recognition.
Chirality 2015, 27, 667-684 (invited article on Special Issue Chirality in Separation Science and Molecular
Recognition).
10
ABSTRACT Halogenated chiral molecules have become important in
several fields of science, industry, and society as drugs, natural
compounds, agrochemicals, environmental pollutants, synthetic products,
and chiral supports. Meanwhile, the perception of the halogen moiety in
organic compounds and its role in recognition processes changed. Indeed,
the recognition of the halogen bond as an intermolecular interaction
occurring when the halogen acts as a Lewis acid had a strong impact,
particularly in crystal engineering and medicinal chemistry. Due to this
renewed interest in the potentialities of chiral organohalogens, here we
focus on selected recent applications dealing with enantioseparations of halogenated compounds on
polysaccharide-based chiral stationary phases (CSPs), widely used in liquid chromatography (LC). In
particular, recently the first case of halogen bonding-driven high-performance LC (HPLC) enantioseparation
was reported on a cellulose-based CSP. Along with enantioseparations performed under conventional
HPLC, representative applications using supercritical fluid chromatography (SFC) are reported.
2014 29. Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
High-performance liquid chromatography enantioseparation of polyhalogenated 4,4’-bipyridines on
polysaccharide-based chiral stationary phases under multimodal elution.
J. Sep. Sci. 2014, 37, 2481-2489.
ABSTRACT An investigation on the high-
performance liquid chromatography
enantioseparation of 12 polyhalogenated 4,4’-
bipyridines on polysaccharide-based chiral
stationary phases is described. The overall study
was directed toward the generation of efficient
separations in order to obtain pure atropisomers
that will serve as ligands for building homochiral
metal organic frameworks. Four coated columns-
namely, Lux Cellulose-1, Lux Cellulose-2, Lux
Cellulose-4, and Lux Amylose-2-and two immobilized columns-namely, Chiralpak IC and IA-were used under
normal, polar organic, and reversed-phase elution modes. Moreover, Chiralcel OJ was considered under
normal-phase and polar organic conditions. The effect of the chiral selector and mobile phase composition
on the enantioseparation, the enantiomer elution order and the beneficial effect of nonstandard solvents
were studied. The effect of water in the mobile phase on the enantioselectivity and retention was
investigated and retention profiles typical of hydrophilic interaction liquid chromatography were observed.
Interesting phenomena of solvent-induced enantiomer elution order reversal occurred under normal-
phasemode. All the considered 4,4’-bipyridines were enantioseparated at the multimilligram level.
11
28. Peluso, P.; Mamane, V.; Cossu, S.
Homochiral metal-organic frameworks and their application in chromatography enantioseparations.
J. Chromatogr. A 2014, 1363, 11-26 (invited review on Special Issue Enantioseparation 2014).
ABSTRACT The last frontier in the chiral stationary
phases (CSPs) field for chromatography
enantioseparations is represented by homochiral metal-
organic frameworks (MOFs), a class of organic-
inorganic hybrid materials built from metal-connecting
nodes and organic-bridging ligands. The modular nature of these materials allows to design focused
structures by combining properly metal, organic ligands and rigid polytopic spacers. Intriguingly, chiral
ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure
of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins,
polysaccharides) which are characterized by a definite helical sense associated with the chirality of their
building blocks (amino acids or sugars). Nowadays, robust and flexible materials characterized by high
porosity and surface area became available by using preparative procedures typical of the so-called reticular
synthesis. This review focuses on recent developments in the synthesis and applications of homochiral
MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy,
interesting results have been produced and a critical overview of the 12 reported applications for gas
chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader
approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this
field is provided.
27. Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
Insights into the impact of shape and electronic properties on the enantioseparation of polyhalogenated 4,4’-
bipyridines on polysaccharide-type selectors. Evidence of stereoselective halogen bonding interactions.
J. Chromatogr. A 2014, 1345, 182-192.
ABSTRACT Starting from the high-performance liquid chromatography
(HPLC) enantioseparation data collected by using twelve
polyhalogenated 2,2’-dichloro-3-substituted-5,5’-dihalo-4, 4’-bipyridines
as test probes on seven polysaccharide-based chiral stationary phases
(CSPs) under multimodal elution, the impact of substitution pattern,
shape and electronic properties of the molecules on the separation
behaviour was investigated through the evaluation of the
chromatographic parameters (k, α, Rs) and molecular properties
determined by means of quantum chemistry calculations. The
computational/chromatographic screening furnished relevant structure-
chromatographic behaviour relationships and some molecular interactions involved in the chiral
discrimination process could be identified. In particular, a halogen bonding interaction (I•••O) could
reasonably explain the high enantioseparation (α = 1.80, Rs = 8.2) observed for the 2,2’-dichloro-3,5’-diiodo-
12
5-bromo-4,4’-bipyridine on Lux Cellulose-1. To the best of our knowledge, this is the first report supporting
the involvement of a stereoselective halogen bonding interaction in polysaccharide-based CSPs. Moreover,
having at disposal a sufficient set of data, the unknown absolute configurations of the eluted enantiomers of
3-methyl-, 3-thiomethyl- and 3-diphenylphosphinoyl-2,2’-dichloro-5,5’-dibromo-4,4’-bipyridines could be
deduced by chromatographic correlation with the enantiomer elution order (EEO) of the related compounds
of known absolute configuration.
2013 26. Peluso, P.; Cossu, S.
Comparative HPLC enantioseparation of thirty six aromatic compounds on four columns of the Lux® series.
Impact of substituents, shapes and electronic properties.
Chirality 2013, 25, 709-718.
ABSTRACT With the aim to define a combined
computational/chromatographic empirical approach useful for
the high-performance liquid chromatography (HPLC) method
development of new chiral compounds, 36 racemic aromatic
compounds with different chemical structures were used as test
probes on four polysaccharide-based chiral stationary phases
(CSPs) of the Lux series, namely Lux Cellulose-1, Lux
Cellulose-2, Lux Cellulose-4, and Lux Amylose-2, using
classical n-hexane/2-propanol mixtures as mobile phase.
Electrostatic potential surfaces (EPSs) determined using Density
Functional Theory (DFT) calculations were used to derive size, shape, and electronic properties of each
analyte. Then a comparative HPLC screening was carried out in order to evaluate the impact of substituents,
shapes, and electronic properties of the analytes on the chromatographic behavior as the column changes.
The four CSPs showed good complementary recognition ability. The elution sequence was determined in 30
cases out of 36. The success rate to afford baseline separations (Rs≥1.5) was estimated: 29 compounds out
of 36 showed baseline enantioseparation on at least one of the four selected CSPs. The combined
computational chromatographic screening furnished useful collective structure-chromatographic behavior
relationships and a map of the chiral discrimination abilities of the considered CSPs towards the analytes.
On this basis, the chromatographic behavior of new analytes on a set of polysaccharide-based CSPs can be
mapped through the qualitative correlation of chromatographic parameters (k, α, Rs) to computed molecular
properties of the analytes.
25. Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
Optimization of the HPLC enantioseparation of 3,3’-dibromo-5,5’-disubstituted-4,4’-bipyridines using
immobilized polysaccharide-based chiral stationary phases.
J. Sep. Sci. 2013, 36, 2993-3003.
13
ABSTRACT The HPLC enantioseparation of nine
atropisomeric 3,3’,5,5’-tetrasubstituted-4,4’-bipyridines
was performed in normal and polar organic (PO) phase
modes using two immobilized polysaccharide-based
chiral columns, namely, Chiralpak IA and Chiralpak IC.
The separation of all racemic analytes, the effect of the
chiral selector, and mobile phase (MP) composition on
enantioseparation and the enantiomer elution order
(EEO) were studied. The beneficial effect of
nonstandard solvents, such as tetrahydrofuran (THF), dichloromethane (DCM), and methyl t-butyl ether on
enantioseparation was investigated. All selected 4,4’-bipyridines were successfully enantioseparated on
Chiralpak IA under normal or POMPs with separation factors from 1.14 to 1.70 and resolutions from 1.3 to
6.5. Two bipyridines were enantioseparated at the multimilligram level on Chiralpak IA. Differently, Chiralpak
IC was less versatile toward the considered class of compounds and only five bipyridines out of nine could
be efficiently separated. In particular, on these columns, the ternary mixture n-heptane/THF/DCM (90:5:5) as
MP had a positive effect on enantioseparation. An interesting phenomenon of reversal of the EEO depending
on the composition of the MP for the 3,3’-dibromo-5,5’-bis-(E)-phenylethenyl-4,4’-bipyridine along with an
exceptional enantioseparation for the 3,3’-dibromo-5,5’-bis-ferrocenylethynyl-4,4’-bipyridine (α = 8.33, Rs =
30.6) were observed on Chiralpak IC.
24. Mamane, V.; Aubert, E.; Peluso, P.; Cossu, S.
Lithiation of prochiral 2,2’-dichloro-5,5’-dibromo-4,4’-bipyridine as a tool for the synthesis of chiral
polyhalogenated 4,4’-bipyridines.
J. Org. Chem. 2013, 78, 7683-7689.
ABSTRACT Lithiation of the achiral
tetrahalogenated 4,4′- bipyridine 1 with alkyllithiums
was investigated. n-BuLi was found to induce either
the chlorine-directed deprotolithiation reaction
alone or with a concomitant halogen−lithium
exchange furnishing after iodine trapping chiral 4,4′-bipyridines 2 and 6, respectively. The role of n-BuLi in
the deprotolithiation process of 1 was elucidated on the basis of isolated secondary derivatives. After
deprotolithiation, the lithiated species could be trapped by different electrophiles such as MeI, TMSCl,
MeSSMe, R3SnCl (R = Me or n-Bu), and PPh2Cl. Moreover, 4,4′-bipyridine 2 was submitted to cross-
coupling reactions (Suzuki and Sonogashira) which occurred selectively at the carbon−iodine bond. All
compounds of this new family of atropisomeric 4,4′-bipyridines were separated by chiral HPLC (high-
performance liquid chromatography), and the absolute configurations of obtained enantiomers were mainly
assigned by XRD (X-ray diffraction) using anomalous dispersion.
14
2012 23. Mamane, V.; Aubert, E.; Peluso, P.; Cossu, S.
Synthesis, resolution, and absolute configuration of chiral 4,4′-bipyridines.
J. Org. Chem. 2012, 77, 2579-2583.
ABSTRACT A chiral polyhalogenated 4,4′-bipyridine derivative is described allowing an easy access to a
new family of chiral 4,4′- bipyridines by site-selective cross-coupling reactions. The absolute configurations of
all the HPLC separated enantiomers were determined by X-ray diffraction and electronic circular dichroism
coupled with time-dependent density functional theory calculations.
22. Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S.
High performance liquid chromatography enantioseparation of atropisomeric 4,4’-bipyridines on
polysaccharide-type chiral stationary phases: impact of substituents and electronic properties.
J. Chromatogr. A 2012, 1251, 91-100.
ABSTRACT The high performance liquid chromatography (HPLC) enantioseparation of eleven atropisomeric
4,4’-bipyridines was performed in the normal and polar organic phase mode using three cellulose-based
chiral stationary phases (CSPs), namely Lux® Cellulose-1, Lux® Cellulose-2, Lux® Cellulose-4, and two
amylose-based CSPs, Chiralpak® AD-H and Lux® Amylose-2. n-Hexane/2-propanol mixtures and pure
ethanol were employed as mobile phases. The combined use of Chiralpak® AD-H and Lux® Cellulose-2
allowed to enantioseparate all the considered bipyridines. Ten bipyridines were enantioseparated at the
multimilligram level allowing the elution sequence determination of the enantiomers as well as their future
use for the preparation of homochiral metal organic frameworks (MOFs). Moreover, the performance of the
CSPs regarding the same bipyridine was different and dependent on the backbone as well as on the side
chain of the polymer. The impact of substitution pattern, shape and electronic properties of the molecules on
the separation behavior was investigated through the evaluation of retention factors (k), separation factors
(α), resolution (Rs) and molecular properties determined using density functional theory (DFT) calculations.
In this regard, the substituents at the 3,3’,5,5’ positions of the 4,4’-bipyridyl rings exhibited a pivotal role on
the enantioseparation.
2011 21. Peluso, P.; Fabbri, D.; Dettori, M. A.; Delogu, G.; Zambrano, V.; Cossu, C.
High-performance liquid chromatographic enantioseparation of atropisomeric biphenyls on seven chiral
stationary phases.
Curr. Org. Chem. 2011, 15, 1208-1229.
ABSTRACT The HPLC enantioseparation of eight racemic atropisomeric biphenyls on commercially
available polymeric Chiralcel OD-H, Lux Cellulose-1, Lux Cellulose-2, Chiralcel OJ, Lux Amylose-2 and
Chiralpak OT(+) and on the brush-type Whelk-O1 columns, both in normal-phase mode and in polar organic
solvent mode, has been investigated. The attempts to enantioseparate the selected biphenyls on Whelk-O1
were unsuccessful. All compounds were well resolved on almost one of the polymeric columns. Lux
15
Cellulose-2 showed to be suitable for enantioseparation of all biphenyls. The effect of mobile phase,
temperature, type of chiral selector and analyte structure on enantioseparation are examined and discussed.
2-Propanol and ethanol were employed as mobile phase modifiers and their influence on the retention and
enantioseparation was investigated. Also a ternary mobile phase (n-hexane/2-propanol/methanol 91:6:3)
was employed to test the separation of the eight biphenyls. In some cases, the elution with pure ethanol
provided good enantioseparation in shorter elution times. The experimental data evidenced the
complemental chiral recognition capabilities of polysaccharide-based CSPs. Noteworthy, Lux Cellulose-1
and Chiralcel OD-H contain the same chiral selector, but the first one exhibited higher retention factors. The
evaluation of chromatographic data provided information about the chiral recognition mechanisms. In this
regard, we report on the effect of ortho and meta biphenyl substituents on the retention and
enantioseparation. In addition, computational evaluation of electrostatic potentials of analytes furnished a
very interesting piece of information about the enantioseparability as well as the chiral recognition
mechanisms on the evaluated chiral selectors.
2009
20. Peluso, P.; Cossu, S.; Moretto, F.; Marchetti, M.
High performance liquid chromatographic enantioseparation of chiral bridged polycyclic compounds on
Chiralcel OD-H and Chiralpak OT(+).
Chirality 2009, 21, 507-518.
ABSTRACT The HPLC enantiomeric separation of 29 racemic bridged polycyclic compounds was examined
on commercially available Chiralcel OD-H and Chiralpak OT(+) columns. The separations were evaluated
under normal-phase mode (hexane containing mobile phase) for Chiralcel OD-H and under normal-phase as
well as under reversed-phase mode (pure MeOH, temperature 58C) for Chiralpak OT(+). Almost all
compounds were resolved either on Chiralcel OD-H or on Chiralpak OT(+), in some cases on both. The use
of trifluoroacetic acid (TFA), as modifier of the hexanic mobile phase, had a beneficial effect on the
enantioseparation of some polar and acidic compounds on Chiralcel OD-H. The influence of small chemical
structural modifications of the analytes on the enantioseparation behavior is discussed. A structure-retention
relationship has been observed on both stationary phases. This chromatographic evaluation may provide
some information about the chiral recognition mechanism: in the case of Chiralcel OD-H, hydrogen bonding,
π-π and distereoselective repulsive are supposed to be the major analyte-CSP interactions. In the case of
Chiralpak OT(+), a reversed-phase enantioseparation could take place through hydrophobic interactions
between the aromatic moiety of the analytes and the chiral propeller structure of the CSP. The synthesis of
some unknown racemic bromobenzobicyclo[2.2.1] analytes is also described.
2006 19. Cossu, S.; Peluso, P.; Moretto, F.; Marchetti, M.
Conversion of γ-substituted bicyclo[2.2.1] (Z)-vinylsulfones to the corresponding (E)-allylsulfones.
Tetrahedron Lett. 2006, 47, 2253-2256.
16
ABSTRACT The preparation of bicyclo[2.2.1] (E)-allylsulfones starting from the corresponding (Z)-
vinylsulfones is described. Starting from 2,3-bis(phenylsulfonyl)norbornadiene 1, the Michael addition of
organometallic reagents followed by the base catalyzed isomerization affords (E)-allylsulfones in high yields.
The procedure allows to obtain vinylidenic norbornenes which are characteristic nuclei of valuable
biologically active compounds.
18. Cossu, S.; Peluso, P.; Alberico, E.; Marchetti, M.
Rhodium catalyzed hydroformylation of 2-phenylsulfonylbicyclo[2.2.1] alkenes: effect of the phenylsulfonyl
group.
Tetrahedron Lett. 2006, 47, 2569-2572.
ABSTRACT The preliminary results of the hydroformylation of 2-phenylsulfonyl substituted norbornene and
norbornadiene derivatives catalyzed by the unmodified Rh(CO)2acac system are presented. The reaction,
occurring under standard oxo conditions, gives polyfunctionalized exo norbornene- and exo
norbornanecarboxaldehydes. The effect of the phenylsulfonyl group has been evaluated: it has been found
that the steric properties of the sulfonyl substituent, more than the electronic ones, influence the
regioselectivity of the process.
17. Cossu, S.; Peluso, P.
Desymmetrization of meso 7-aza-2,3-bis(phenylsulfonyl) bicyclo[2.2.1]hept-2-ene: a re-examination. Kinetic
resolution of racemic 3-arylsulfonyl-7-aza-2-bromobicyclo[2.2.1]hepta-2,5-dienes.
Tetrahedron Lett. 2006, 47, 4015-4018.
ABSTRACT The inexpensive large scale preparation of N-methoxycarbonyl-7-aza-2,3-bis(phenylsulfonyl)
bicyclo[2.2.1]hept-2-ene and the re-examination of its stereoselective desymmetrization are reported.
Moreover, the kinetic resolution of N-protected 3-arylsulfonyl-7-aza-2-bromobicyclo[2.2.1]hepta-2,5-dienes
promoted by (R,R)-hydrobenzoin is described, representing a new tool to fix the absolute stereochemistry of
the 7-azabicyclo[2.2.1] skeleton.
2005 16. Cossu, S.; Peluso, P.
Diastereoselective desymmetrization of meso bis(phenylsulfonyl) polycyclic alkenes promoted by C2
symmetric chiral diolates: direct access to optically pure ketals and ketones.
Org. Chem.: an Indian J. 2005, 1, 1-17.
ABSTRACT The desymmetrization of meso 1,2-bis(phenylsulfonyl) substituted bridged polycyclic alkenes
promoted by C2 symmetric chiral diolates is reported. The phenylsulfonyl group exerts an
electronwithdrawing effect onto the C-C double bond, making the alkenylic function a good Michael acceptor:
enantiotopic Csp2 react with the enantiopure nucleophile which has been used in stoichiometric amount. The
stereoselective process leads to the formation of optically pure α-phenylsulfonylsubstituted polycyclic ketals,
17
which are valuable intermediate in the synthesis of polycyclic α-phenylsulfonylketones and ketones. The
kinetic resolution of a racemic mixture of a tolylsulfonylsubstituted polycyclic alkene is also reported.
15. Cossu, S.; Peluso, P.
Stereoselective desymmetrizations: role of symmetry, stereofacial discrimination and steric effects.
Org. Chem.: an Indian J. 2005, 1, 18-37.
ABSTRACT A stereoselective desymmetrization is a symmetry breaking synthetic operation and represents
a powerful synthetic tool not only for the preparation of new chiral synthons or building blocks, but also for
the applications in the target oriented synthesis, yielding enantiomerically enriched products. In this
microreview, after a brief historical overview of the origin of the method, through representative exxamples
that go back to the last six years, we describe the role of molecular symmetry and steric effects on the
stereotopic and stereofacial discrimination mechanisms. The most effective procedures to perform a
stereoselective desymmetrization of a non-chiral symmetric compound by nonenzymatic or enzymatic
methods are here presented.
2002 14. Samaritani, S.; Peluso, P.; Malanga, C.; Menicagli, R.
Selective amination of cyanuric chloride in the presence of 18-crown-6.
Eur. J. Org. Chem. 2002, 1551-1555.
ABSTRACT An interpretation of the role of 18-crown-6 in the selective di- and trialkylamination of 2,4,6-
trichloro-1,3,5-triazine is reported, and the usefulness of the procedure is shown.
13. Peluso, P.; Greco, C.; De Lucchi, O.; Cossu, S.
Synthesis of 2-mono- and 2,3-disubstituted polycyclic alkenes.
Eur. J. Org. Chem. 2002, 4024-4031.
ABSTRACT A range of mono- and disubstituted (−Br, −Cl, −SPh, −SO2Ph) polycyclic alkenes has been
prepared starting from alkenes by inexpensive and high-yielding synthetic routes.
12. Peluso, P.; De Lucchi, O.; Cossu, S.
Role of copper in the stereoselective metal-promoted cyclotrimerisation of polycyclic alkenes.
Eur. J. Org. Chem. 2002, 4032-4036.
ABSTRACT Copper-mediated stereoselective cyclotrimerisation of polycyclic alkenes is reported. The
mechanism involved provides strong support for the involvement of a Cu III intermediate in cross-coupling
reactions of sp2-carbon atoms.
18
2001 11. Cossu, S.; De Lucchi, O.; Peluso, P.; Volpicelli, R.
Improved selective synthesis of (Z)- and (E)-1,2-bis(phenylsulfonyl)chloroethylene.
Synth. Commun. 2001, 31, 27-32.
ABSTRACT The preparation of the title compounds (Z)- and (E)-1, which are synthetic substitutes for the
unstable bis(phenylsulfonyl)acetylene and key reagents for the asymmetric preparation of polycyclic ketones,
has been revisited and improved. Starting from inexpensive materials such as trichloroethylene, thiophenol,
and hydrogen peroxide, (Z)- and (E)-1 are selectively obtained in multigram quantity in 52% overall yields.
10. Ballini, R.; Bosica, G.; Cossu, S.; De Lucchi, O.; Peluso, P.
Observations in the alkylation of β-acetalic carbanions: monoalkylation vs. dialkylation and elimination.
Tetrahedron 2001, 57, 4461-4465.
ABSTRACT The reaction with methyl iodide and a base (t-BuOK) of 1,3-dioxolanes and 1,3-dithiolanes
substituted at the β-position with an electron-withdrawing substituent (EWG = -CO2Me, -SO2Ph, -SO2Ph-p-
NO2, SO2Ph-o-NO2) leads to mono- or dialkylated or ring opened products in good yield.
9. Cossu, S.; De Lucchi, O.; Paulon, A.; Peluso, P.; Zonta, C.
Anti-selective Heck cyclotrimerisation of polycyclic bromoalkenes.
Tetrahedron Lett. 2001, 42, 3515-3518.
ABSTRACT Vinyl halides can react as both substrate and reagent in the Heck reaction. In the case of
bicyclic vinyl halides, the reaction leads to cyclotrimers through an anti-selective process.
8. Cossu, S.; Cimenti, C.; Peluso, P.; Paulon, A; De Lucchi, O.
Enantiomeric discrimination in a reiterative domino coupling process: Cu (I)-mediated syn-cyclotrimerization
of racemic polycyclic trimethylstannyl bromonorbornadienes.
Angew. Chem. Int. Ed. 2001, 40, 4086-4089.
ABSTACT Herein we report a new CuI-mediated cyclotrimerization of racemic 3-bromo-2-
trimethylstannylalkenes which affords syn cyclotrimers through a reiterative enantiomeric discrimination
process.
2000 7. Peters, K.; Peters, E.-M.; Volpicelli, R.; Cossu, S.; De Lucchi, O.; Peluso, P.
Crystal structure of 2β,3β-bis(phenylsulfonyl)-2α-chlorobicyclo[2.2.1]hepta-5-ene, C7H7(SO2C6H5)2Cl.
Z. Kristallogr. NCS 2000, 215, 33-34.
6. Peters, K.; Peters, E.-M.; Volpicelli, R.; Cossu, S.; De Lucchi, O.; Peluso, P.
19
Crystal structure of 3α,4α-4',5'-diphenyl-3-(phenylsulfonyl)1R-[1α,2(4'R*,5'R*)spiro]bicyclo[2.2.1]hept-5-
ene,2'[1,3]dioxolane,[(C6H5SO2)C7H7][C2H2O2(C6H5)2].
Z. Kristallogr. NCS 2000, 215, 231-232.
5. Cossu, S.; De Lucchi, O.; Peluso, P.; Volpicelli, R.
Li+ and Na+ switch of enantioselectivity in the desymmetrisation of polycyclic bis(phenylsulfonyl)alkenes by
chiral alcohols.
Tetrahedron Lett. 2000, 41, 7263-7266.
ABSTRACT A complete switch of enantioselectivity is obtained in the desymmetrisation reaction of polycyclic
bis(phenylsulfonyl)alkenes by the change of the base from n-BuLi to NaH, thus allowing convenient access
to either enantiomer of polycyclic ketones with the same chiral auxiliary.
1999 4. Zonta, C.; Cossu, S.; Peluso, P.; De Lucchi, O.
Stereochemistry of the cyclotrimerisation of enantiopure polycyclic bromostannylalkenes: mechanistic
considerations on the coupling of alkenyl stannanes by copper (II) nitrate.
Tetrahedron Lett. 1999, 40, 8185-8188.
ABSTRACT The cyclotrimerisation of enantiopure l-bromo-2-trimethylstannylbenzonorbornadiene 2, contrary
to the expectations, affords predominantly the trimer anti-4. This observation suggests that the reaction
proceeds mainly via a Sn-Sn coupling to produce the dimer anti-5 and a tin-copper product that triggers
halogen-metal exchange on the dimer thus allowing a second coupling with the starling reagent eventually
leading to the anti- trimer. The little but consistent formation of the isomer syn-4 and meso dimer 5 can arise
from a racemisation of the bromine-copper-tin intermediate possibly via an alkyne structure.
3. Cossu, S.; De Lucchi, O.; Peluso, P.; Volpicelli, R.
Enantioselective synthesis of polycyclic ketones by desymmetrisation of bis(phenylsulfonyl)alkenes with
chiral alcoholates. Control of the absolute configuration by simple modification of the chiral auxiliary.
Tetrahedron Lett. 1999, 40, 8705-8709.
ABSTRACT Treatment of polycyclic bis(phenylsulfonyl)alkenes with chiral alcoholates, followed by acidic
work-up, affords enantioselectively ct-phenylsulfonyl ketones. The enantioselectivity is total with
monomethylated hydrobenzoin and of opposite configuration with respect to that obtained with hydrobenzoin
itself. Thus, starting from a bis(phenylsulfonyl)alkene, it is possible to obtain either the R or S polycyclic
ketone by the use of the same chiral auxiliary (hydrobenzoin) and a simple modification (methylation of one
of the hydroxy functions).
1997 2. Uccello-Barretta, G.; Iuliano, A.; Menicagli, R.; Peluso, P.; Pieroni, E.; Salvadori, P.
1,3,5-Triazine multiselector systems: new tools for chiral discrimination.
20
Chirality 1997, 9, 113-121.
ABSTRACT 2-Hexylamino-4-[(S)-1-(1-naphthyl)ethylamino]-6-L-valyl-L-valyl-L-valine isopropylester-1,3,5-
triazine (1), a molecule characterized by two different chiral selectors, and 2-hexylamino-4,6-bis-L-valyl-L-
valyl-L-valine isopropylester-1,3,5-triazine (2) and 2-ethoxy-4-hexylamino-6-[(S)-1-(1-naphthyl)ethylamino]-
1,3,5-triazine (3), systems in which a single kind of chiral selector is present, have been prepared. The
enantiodiscriminating ability in solution of the three compounds toward the N-3,5-dinitrobenzoyl derivatives of
1-phenylethylamine (4) or valine methylester (5) has been investigated by 1H nuclear magnetic resonance
(NMR) spectroscopy: 1 shows an improved versatility, relative to 2 and 3, as a chiral solvating agent for NMR
spectroscopy. On the basis of the indications obtained, the usefulness of 2-chloro-4-[(S)-1-(1-
naphthyl)ethylamino]-6-L-val-L-val-L-valine isopropylester-1,3,5-triazine (1a), a direct precursor of 1, as chiral
solvating agent for the determination by NMR of the enantiomeric compositions of derivatives of amines,
amino alcohols, amino acids, and carboxyl acids bearing a 3,5-dinitrophenyl moiety, has been demonstrated.
1994 1. Menicagli, R.; Malanga, C.; Peluso, P.
Selective mono- or dialkoxylation of 2,4,6-trichloro-1,3,5-triazine in solid-liquid phase transfer conditions.
Synth. Commun. 1994, 24, 2153-2158.
ABSTRACT In solid-liquid phase transfer conditions, both the primary and the secondary alcohols react
cleanly with 2,4,6-trichloro-1,3,5-triazine to give the corresponding mono or dialkoxy derivatives depending
on the reagent molar ratio.
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