Formazione

CURRICULUM
Gianni Palmieri
Formazione
Gianni Palmieri, nato a Treia (Marche, Italia) nel 1947, si iscrive all’Università di Camerino
dove si laurea in Chimica nel 1972. Inizia la sua carriera scientifica all’Università di Roma
“La sapienza” come borsista CNR e contrattista ministeriale, nel gruppo dei Professori
Domenico Misiti e Luciano Caglioti, dove viene confermato nella posizione di Assistente
universitario nel 1975. Nel 1978 si trasferisce come Professore incaricato all’Università di
Camerino dove viene chiamato come Professore Associato di Chimica Organica (1985) e
successivamente Professore Straordinario (2004). I suoi attuali interessi nella ricerca
scientifica sono nel campo della stereoselezione in sintesi organica sviluppando nuove
metodologie ed applicazioni, con particolare interesse verso i processi ecosostenibili. In
particolare ha sviluppato nuove metodologie per la sintesi regio- e stereoselettiva di
sistemi enamminonici e derivati analoghi, adottando la chimica dei carbanioni con
l’impiego di reattivi organometallici. Ha inoltre studiato la reattività di tali sistemi
enamminonici che sono stati convenientemente utilizzati nella sintesi asimmetrica per la
preparazione di composti biologicamente attivi in forma enantiopura (ammine, fosfine,
alcoli polifunzionali). I derivati amminopolioli così ottenuti sono stati ampiamente studiati
come chelanti nella preparazione di catalizzatori metallici chirali che a loro volta
promuovono reazioni di riduzione ed alchilazione con altro grado di stereoselettività. Gli
stessi amminopolioli ed amminofosfine trovano inoltre applicazione nella preparazione di
materiali cromatografici innovativi per la ricognizione chirale.
Education & Training
Born in Treia (Marche, Italy) in 1947, Gianni Palmieri began his university training in
University of Camerino where he obtained his laurea degree in Chemistry in 1972. He
began his scientific career to te University “La Sapienza”, Rome as Borsista CNR and
subsequently as Contrattista ministeriale working in the group of Professor Domenico
Misiti and Luciano Caglioti, and he was confirmed in the position of university Assistant in
1975. In 1978, joined the University of Camerino were he become (1985) Associate
Professor of Organic Chemistry and subsequently (2004) full Professor of Organic
Chemistry. His current research interest are in the field of the stereoselection in organic
synthesis in the developing of new methodologies and applications, with particular interest
toward the ecosustainable process. In particular he has developed new methodologies for
the regio- and stereosective synthesis of enaminonic systems and analogous derivatives,
adopting the carbanion chemistry and with the employment of organometallic reagents. He
has studied besides the reactivity of the same enaminonic systems that resulted to be
convenient starting materials in the asymmetric synthesis for the preparation of
enantiopure biologically active compounds (amines, phosphines, polifunctional alcohols).
The aminopoliols in this way obtained have been studied as ligands and broadly used in
the preparation of chiral metallic catalysts promoters of reactions of reduction and
alkylation with high degree of stereoselectivity.
The same aminopoliols and the
aminophosphines find besides application in the preparation of innovative
chromatographic materials for the chiral recognition.
Esperienze di Ricerca e Sviluppo

Sviluppo di nuove metodologie stereoselettive nella formazione di legami C-C e
nella funzionalizzazione di molecole organiche, con particolare interesse verso i
processi ecosostenibili.

Design e sintesi di molecole polifunzionali stereodefinite quali unità fondamentali di
sostanze biologicamente attive e di leganti per la catalisi enantioselettiva

Strutture molecolari e materiali cromatografici innovativi per la ricognizione chirale
Research Experience

Developing of new stereoselective methodologies in the formation of C-C bonds
and in the functionalization of organic molecules, with particular interest toward the
ecosusteinable process.

Design and synthesis of stereodefined polyfunctional molecules as fundamental
units of biologically active substances and of ligands for enantioselective catalysis.

Molecular structures and innovative chromatographic materials for the chiral
recognition.
Competenze
Uso delle tecniche per la sintesi stereoselettiva con l’impiego della chimica dei carbanioni
e di reagenti organometallici, per la formazione di legami C-C e per le riduzioni
stereoselettive. Tecniche per la purificazione e la separazione cromatografica di composti
chirali. Determinazione della struttura mediante tecniche spettroscopiche moderne, con
l’attribuzione della stereochimica e della purezza ottica dei composti. Uso della
modellistica
molecolare come ausilio nella razionalizzazioni delle proprietà
spettroscopiche dei composti, per la determinazione della loro struttura stereochimica e la
formulazione di ipotesi sui meccanismi di reazione (analisi conformazionale,
diastereoselettività nello stato di transizione).
SKILLS
Use of the techniques for the stereoselective synthesis with the employment of carbanion
chemistry and of organometallic reagents, for the formation of C-C bonds and for
stereoselective reductions. Techniques for purification and chromatographic separation of
chiral compounds. Determination of the structure through modern spectroscopic
techniques, with the attribution of the stereochemistry and the optical purity of the
compounds. Use of molecular modelling as aid in the rationalizations of spectroscopic data
of the compounds, in the aim of determination of their stereochemical structure and of the
formulation of hypothesis on the reaction mechanisms (conformational analysis,
diastereoselectivity in the transition state).
ALTRO
Carichi didattici:

Chimica Organica 1 e laboratorio (classe 21) dal 1984

Stereochimica Organica (classe 62/S) dal 1979

Chimica Organica (classe 6/S) dal 2003

Biochimica Strumentale (Sc. Spec. Biochimica Clinica) dal 1987
Courses:

Organic Chemistry 1 and Laboratory (class 21) since 1984

Organic sterochemistry (class 62/S) since 1979

Organic Chemistry (class 6/S) since 2003

Instrumental Biochemistry (Sc. Spec. Biochimica Clinica) since 1987
Publications
1.
C. CIMARELLI, G. PALMIERI: Stereoselective Reduction of Enantiopure -Enamino Esters by
Hydride; a Convenient Synthesis of Both Enantiopure -Amino Esters. J. Org. Chem., 1996, 61,
5557-5563.
2.
M. CAMALLI, C. CIMARELLI, G. PALMIERI: A Directed Stereoselective Aldol Reaction: Simple
Synthesis of Enantiopure -Hydroxy--enamino Ketones by Condensation of Homochiral Enamino Ketones with Aldehydes and Ketones. Tetrahedron: Asymmetry, 1996, 7, 2099-2112.
3.
C. CIMARELLI and G. PALMIERI: Enaminones: Useful starting materials for the preparation of
heterocycles. Recent Res. Devel. in Organic Chem., 1997, 1, 179-189.
4.
C. CIMARELLI and G. PALMIERI: Stereoselective Synthesis of 5-Alkyliden-6-aminotetrahydro-2pyranones Through an Unexpected Isomerization of the Hydroxytetrahydro-2-pyridinones Obtained
by the Selective Reduction of Acylated Enaminones. Tetrahedron, 1998, 54, 915-926.
5.
C. CIMARELLI and G. PALMIERI: Alkylation of Dianions Derived from 2-(1-Iminoalkyl) Phenols:
Synthesis of Functionalized 2-Acyl Phenols. Tetrahedron, 1998, 54, 15711-15720.
6.
G. PALMIERI: Synthesis of Enantiopure o-Hydroxybenzylamines by Stereoselective Reduction of
2-Imidoylphenols: Application in the Catalytic Enantioselective Addition of Diethylzinc to Aldehydes.
Eur. J. Org. Chem. 1999, 805-811.
7.
C. CIMARELLI and G. PALMIERI: Acylation of o-Imidoylphenol Lithium Dianions: Synthesis of 4HChromen-4-ylidene Amines. Tetrahedron, 2000, 56, 475-478.
8.
D’ACQUARICA, F. GASPARRINI, D. MISITI, G. ZAPPIA, C. CIMARELLI, G. PALMIERI, A. CAROTTI,
S. CELLAMARE, C. VILLANI: Application of a Chiral Stationary Phase Containing the New
Glycopeptide A-40,926 in the Direct Chromatographic Resolution of -Amino Acids. Tetrahedron:
Asymmetry, 2000, 11, 2375-2385.
9.
C. CIMARELLI, G. PALMIERI: Asymmetric Reduction of Enantiopure Imines with Zinc Borohydride:
Stereoselective Synthesis of Chiral Amines. Tetrahedron: Asymmetry, 2000, 11, 2555-2563.
10.
G. PALMIERI: A Practical o-Hydroxibenzylamines Promoted Enantioselective Addition of
Dialkylzincs to Aldehydes with Asymmetric Amplificaion. Tetrahedron: Asymmetry, 2000, 11, 33613373.
11.
C. CIMARELLI, A. MAZZANTI, G. PALMIERI, E. VOLPINI: Solvent-Free
Asymmetric
Aminoalkylation of Electron-Rich Aromatic Compounds: Stereoselective synthesis of
aminoalkylnaphthols by crystallization-induced asymmetric transformation. J. Org. Chem., 2001,
4759-4765.
12.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: Reduction of 4H-Chromen-4-ylidene Amines: Synthesis
of 2-[(1-Aminoalkyl)-3-Aryl-2-propenyl] Phenols. Tetrahedron, 2001, 6809-6814.
13.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: Ready N-Alkylation of Enantiopure Aminophenols:
Synthesis of Tertiary Aminophenols. Tetrahedron, 2001, 6089-6096.
14.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: Synthesis of Enantiopure 2-Aminoalkylphenols by
Stereoselective Addition Of Grignard Ragents To Chiral
2-Imidoylphenols. Tetrahedron:
Asymmetry, 2002, 13, 2011-2018.
15.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: A practical stereoselective synthesis of secondary and
tertiary aminonaphthols: chiral ligands for enantioselective catalysts in the addition of diethylzinc to
benzaldehyde. Tetrahedron: Asymmetry, 2002, 13, 2417-2426.
16.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: Stereoselective Alkylation of Chiral 2-Imidoylphenols
with Organolithium Reagents: Synthesis of Enantiopure 2-Aminoalkylphenols. J. Org. Chem., 2003,
68, 1200-1206.
17.
E. FORESTI, G. PALMIERI, M. PETRINI, R. PROFETA: Highly diastereoselective addition of
nitromethane anion to chiral -amidoalkylphenyl sulfones. Synthesis of optically active -amino
acid derivatives. Org. Biomol. Chem. 2003, 1, 4275-4281.
18.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: The reaction of -enaminoesters with organolithium
reagents: a convenient method for the regioselective synthesis of enaminoketones. Tetrahedron
Lett., 2004, 45, 6629-6631.
19.
C. CIMARELLI, S. GIULI, G. PALMIERI: One-pot addition/reduction procedure for the synthesis of
-amino alcohols from -enamino ketones. Eur. J. Org. Chem. 2006, 1017-1022.
20.
C. CIMARELLI, G. PALMIERI: Chemo- and stereoselective reduction of enaminones for the
preparation of biologically active compounds. ARKIVOC 2006, 104-126.
21.
C. CIMARELLI, S. GIULI, G. PALMIERI: Stereoselective synthesis of enantiopure -aminoalcohols
by reduction of chiral -enaminoketones. Tetrahedron: Asymmetry 2006, 17, 1308-1317.
22.
C. CIMARELLI, G. PALMIERI, E. VOLPINI: Regio- and stereoselective double alkylation of enamino esters with organolithium reagents followed by one-pot reduction: convenient method for
the synthesis of tertiary -amino alcohols. Tetrahedron 2006, 62, 9423-9432.
23.
L. CAPPANNINI, C. CIMARELLI, S. GIULI, G. PALMIERI, M. PETRINI: Stereoselective synthesis
of vicinal aminodiols, diamines and diamminols by use of enantiopure aldehydes in the threecomponent aromatic Mannich type reaction. Tetrahedron: Asymmetry 2007, 18, 1022-1029.