Università degli Studi di Trieste
Dipartimento di Scienze Chimiche
ORGANIC CHEMISTRY Group
 
e-mail
Teaching activities:
 
Prof. Giuliana Pitacco
Full Professor
gpitacco@units.it
Organic Chemistry 1, Environmental Chemistry, Spectroscopic Methods in Organic Chemistry
Prof. Patrizia Nitti
Associate Professor
pnitti@units.it
Organic Chemistry, Biotransformations, Organic Chemistry Laboratory
Prof. Fulvia Felluga
Associate Professor
ffelluga@units.it
Organic Chemistry, Introduction to Organic Spectroscopy
Dr. Cristina Forzato
 Assistant
Professor
cforzato@units.it
Heterocyclic Chemistry, Natural Products Chemistry
 
Bioconversions

Chiral non racemic γ-lactones, either isolated or policondensed , are widely present in nature as pheromones, flavourings and other natural products. γ-Lactones are also versatile building blocks for the synthesis of bioactive molecules.
The organic chemistry group is involved in the synthesis of optically active γ-butyrolactones mediated by biotransformation processes, using both yeasts and purified enzymes, in particular in the synthesis of paraconic acids, a class of γ-lactones bearing a carboxylic group at the β carbon.
Chemoenzymatic methodologies are also applied to the asymmetric synthesis of optically active functionalized γ-butyrolactams, which are successively converted into analogs of γ-aminobutiric acid, the major inhibitory neurotransmitter in the mammals. In this context, new and convenient syntheses of the pharmacologically active GABA analogs Baclofen and Pregabalin, widely used in therapy for the treatment of neurological diseases, have been developed recently.

Absolute configuration

Particular attention is given to the assignment of the absolute configuration of the new compounds using several approaches such as X-ray, NMR analysis, Circular Dichroism, computational calculations of optical rotatory power and electronic circular dichroism.

Organocatalysis

The organocatalysis has opened new perspectives for the asymmetric synthesis of enantiomerically and diastereomerically bioactive compounds, such as antibiotics, antitumorals and painkillers.
Recently, the organic chemistry group approached the organocatalysis studying the organocatalysed asymmetric Michael reaction between dicarbonylic compounds and different nitroolefins, using chiral amines as catalysts. The products of the reaction are interesting cyclopentanone derivatives, obtained with very high diastereomeric and enantiomeric excess, as well as nitroalkylated products, depending on the organocatalyst used.

Recent Publications
 
2005 G.M. Bonora, S. Drioli, C. Forzato, P. Nitti, G. Pitacco, Baker's yeast reduction of PEG-linked acetoacetate  Lett. Org. Chem. 2 , 89 (2005).
  D. Marchesan, S. Coriani, C. Forzato, P. Nitti, G. Pitacco, K. Ruud, Optical rotation calculation of a highly flexible molecule: the case of paraconic acid J. Phys. Chem. A 109, 1449 (2005).
  F. Berti, C. Forzato, P. Nitti, G. Pitacco, E. Valentin, A study of the enantiopreference of Lipase PS ( Pseudomonas cepacia ) towards dihydro-5-alkyl-4-hydroxymethyl-2(3H)- furanones Tetrahedron: Asymmetry 16, 1091 (2005).
  F. Felluga, V. Gombac, G. Pitacco and E. Valentin, A short and convenient chemoenzymatic synthesis of both enantiomers of 3-PhenylGABA and 3-(4-chlorophenyl)GABA ( Baclofen ) Tetrahedron: Asymmetry 16, 1341 (2005).
  C. Forzato, G. Furlan, P. Nitti, G. Pitacco, D. Marchesan, S. Coriani and E. Valentin, A combined experimental and computational strategy in the assignment of absolute configurations of 4-methyl-5-oxo-tetrahydrofuran-3-carboxylic acids and their esters Tetrahedron: Asymmetry 16, 3011 (2005).


2006 S. Coriani, A. Baranowska, L. Ferrighi, C. Forzato, D. Marchesan, P. Nitti, G. Pitacco, A. Rizzo, K. Ruud, Solvent effects on the conformational distribution and optical rotation of γ-methyl paraconic acids and esters Chirality 18, 357 (2006).
  O. A. Attanasi, G. Favi, P. Filippone, C. Forzato, G. Giorgi, S. Morganti, P. Nitti, G. Pitacco, E. Rizzato, D. Spinelli, E. Valentin, On the Reactivity of Some 2-Methyleneindolines with β-Nitroenamines, α-Nitroalkenes and 1,2-Diaza-1,3-butadienes, Tetrahedron 62, 6420 (2006).
  F. Felluga, V. Gombac, G. Pitacco, E. Valentin, Chemoenzymatic syntesis of pyrrolidin-2-ones and pyrrolin-2-ones, in Targets in Heterocyclic Systems, Chemistry and Propeties, vol. 9, pp.158-185 (2006).
  F. Felluga, V. Gombac, G. Pitacco, E. Valentin, E. Zangrando, S. Morganti, E. Rizzato, D. Spinelli, G. Petrillo, Condensed 2-pyrrolidinone-1,2-oxazines from the lithium enolate of 1-benzyl-5-oxo-3-pyrrolidinecarboxylic acid and β-aryl, β-nitroenamines. Tetrahedron, 62, 8787 (2006).
  F. Berti, F. Felluga, C. Forzato, G. Furlan, P. Nitti, G. Pitacco and E. Valentin, Chemoenzymatic synthesis of diastereomeric ethyl γ-benzyl paraconates and determination of the absolute configurations of their acids. Tetrahedron: Asymmetry 17, 2344 (2006).
  L. De Buyck, C. Forzato, F. Ghelfi, A. Mucci, P. Nitti, U. M. Pagnoni, A. F. Parsons, G. Pitacco and F. Roncaglia, A new and effective route to (±)-botryodiplodin and (±)-epi-botryodiplodin acetates using a halogen atom transfer Ueno–Stork cyclization. Tetrahedron Letters 47, 7759 (2006).


2007 C. Forzato, G. Furlan, F. Ghelfi, P. Nitti, G. Pitacco, F. Roncaglia and E. Valentin, Lipase-catalysed deacetylation of botryodiplodin acetate. Tetrahedron: Asymmetry 18, 447 (2007).
  F. Felluga, C. Forzato, F. Ghelfi, P. Nitti, G. Pitacco, U. M. Pagnoni and F. Roncaglia, Atom transfer radical cyclization (ATRC) applied to a chemoenzymatic synthesis of Quercus lactones. Tetrahedron: Asymmetry 18, 527 (2007).
  F. Felluga, F. Ghelfi, U. M. Pagnoni, A. F. Parsons, M. Pattarozzi, F. Roncaglia and E. Valentin, A novel short approach to (Z)-Pulchellalactam through transition-metal-catalyzed atom-transfer radical cyclization of 1-isopropylprop-2-enyldichloroacetate. Synthesis 12, 1882 (2007).


2008 F. Felluga, G. Pitacco, E. Valentin, C. D. Venneri, A facile chemoenzymatic approach to chiral non-racemic β-alkyl-γ-aminoacids and 2-alkylsuccinic acids. A concise synthesis of (S)-(+)-Pregabalin. Tetrahedron: Asymmetry 19, 945 (2008).
  C. Forzato, G. Furlan, P. Nitti, G. Pitacco, E. Valentin, E. Zangrando, P. Buzzini, M. Goretti, B. Turchetti, Chemoenzymatic and yeast-catalysed synthesis of diastereomeric ethyl γ-phenyl and γ-(n-pyridyl)paraconates Tetrahedron: Asymmetry 19, 2026 (2008).
  F. Ghelfi, M. Pattarozzi, F. Roncaglia, A. F. Parsons, F. Felluga, U. M. Pagnoni, E.Valentin, A. Mucci, F. Bellesia, Preparation of the maleic anhydride nucleus from dichloro γ-Lactams: focus on the role of the substituent in the functional rearrangement and in the hydrolytic steps. Synthesis, 3131 (2008).


2009F. Berti, C. Forzato, G. Furlan, P. Nitti, G. Pitacco, E. Valentin, E. Zangrando, Synthesis of optically active α-benzyl paraconic acids and their esters and assignment of their absolute configuration Tetrahedron: Asymmetry 20, 313 (2009).
S. Coriani, C. Forzato, G. Furlan, P. Nitti, G. Pitacco, M. Ringholm, K. Ruud, Synthesis, characterization and assignment of the absolute configuration of 4,4-dimethyl-5-oxo-tetrahydrofuran-3-carboxylic acid and its esters: a combined experimental and theoretical investigation. Tetrahedron: Asymmetry20, 1459 (2009).
F. Felluga, W. Baratta, L. Fanfoni, G. Pitacco, P. Rigo, F. Benedetti, Efficient chemoenzymatic synthesis of chiral CNN pincer ligands, J. Org. Chem. 78, 3547 (2009).
A. Bertoli, L. Fanfoni, F. Felluga, G. Pitacco, E. Valentin, Chemoenzymatic synthesis of optically active alpha-methylene-gamma-lactams and gamma-lactones, Tetrahedron: Asymmetry 20, 2305 (2009).


2010 K. Chakrabarty, C. Forzato, P. Nitti, G. Pitacco, E. Valentin, The first kinetic enzymatic resolution of methyl ester of C75. Letters in Organic Chemistry 7, 245 (2010).
F. Felluga, C. Forzato, P. Nitti, G. Pitacco, E. Valentin, E. Zangrando, Application of 1,3-azomethine ylides derived from α-dicarbonyl compounds and L-proline to the synthesis of pyrrolizidines. Journal of Heterocyclic Chemistry 47, 664 (2010).
G. Pitacco, O. A. Attanasi, L. De Crescentini, G. Favi, F. Felluga, C. Forzato, F. Mantellini, P. Nitti, E. Valentin, E. Zangrando, Organocatalyzed synthesis of chiral non-racemic 1,4-dihydropyridazines, Tetrahedron: Asymmetry 21, 617 (2010).
L. Preti, O. A. Attanasi, E. Caselli, G. Favi, C. Ori, P. Davoli, F. Felluga, F. Prati, One pot synthesis of imidazole-4-carboxylates by microwave-assisted 1,5-electrocyclization of azavinylazomethine ylides, Eur. J. Org. Chem. 4312 (2010).
W. Baratta, F. Benedetti, A. Del Zotto, L. Fanfoni, F. Felluga, S. Magnolia, E. Putignano, P. Rigo, Chiral pincer ruthenium and osmium complexes for the fast and efficient hydrogen transfer reduction of ketones, Organometallics 29, 3563 (2010).
F. Felluga, F. Ghelfi, G. Pitacco, F. Roncaglia, e. Valentin, C. D. Venneri, Esterase-mediated synthesis of optically active GABA analogues containing a stereogenic all-carbon quaternary carbon atom, Tetrahedron: Asymmetry 21, 2183 (2010).
A. D'Amora, L. Fanfoni, D. Cozzula, N. Guidolin, E. Zangrando, F. Felluga, S. Gladiali, F. Benedetti, B. Milani, Addressing the poly- to oligo-ketone selectivity in styrene carbonylation catalyzed by palladium/bpy complexes, effect of the 6-alkyl substitution, Organometallics 29, 4472 (2010).


2011R. Casolari, F. Felluga, V. Frenna, F. Ghelfi, A. F. Parsons, D. Spinelli, A green way to gamma-lactams through a copper catalyzed ARGET-ATRC in ethanol and in the presence of ascorbic acid, Tetrahedron 67, 408 (2011).
M. Bregoli, F. Felluga, V. Frenna, F. Ghelfi, U. Pagnoni, A. Parsons, G. Petrillo, D. Spinelli, Synthesis of 4-chloromethyl-3-alkyl-1-RSO2-1H-pyrrol-2(5H)-ones, using a sequential ATRC/[1,2]-elimination, from 2,2-dichloro-N-(2-chloroallyl)-N-RSO2-amides, Synthesis 8, 1267 (2011).
L. Fanfoni, A. Meduri, E. Zangrando, S. Castillon, F. Felluga, B. Milani, New chiral P-N ligands applied for the regio- and stereoselective Pd-catalyzed styrene dimerization, Molecules 16, 1804 (2011).


2012F. Felluga, C. Forzato, F. Ghelfi, P. Nitti, G. Pitacco, E. Valentin, First chemoenzymatic synthesis of (4R,5S)-(+)-2-carboxypyrrolidine-3-acetic acid (CPAA), the nucleus of kainoids amino acids, Chirality 24, 112 (2012).
F. Ghelfi, F. Bellesia, F. D'Anna, F. Felluga, V. Frenna, A. Parsons, F. Reverberi, D. Spinelli, Breakthrough in the alpha-perchlorination of acylchlorides, Synthesis 605 (2012).
 
Cristina Forzato 13/Feb/2012