MARIKA DI BERTO MANCINI

Dottoressa di ricerca

ciclo: XXXV


supervisore: Osvaldo Lanzalunga

Titolo della tesi: Selectivity study in the functionalization of organic compounds promoted by radical and radical-like species

Oxidative C-H functionalization of organic substrates promoted by cheap, eco-friendly and selective systems has received a great attention in recent years, since it allows to convert relatively unreactive bonds, ubiquitous in organic molecules, into functional groups suitable for further transformations. Oxidation of sulfides to sulfoxides is another important process due to the presence of sulfinyl functional group in many natural products and biologically active compounds, like anti-inflammatory or antibiotic drugs. Moreover, sulfoxides are important reagents in organic synthesis: in fact, chiral sulfoxides have been used as auxiliaries in asymmetric synthesis. In this thesis, the use of biomimetic nonheme iron complexes and N-hydroxyphthalimide (NHPI) as efficient and selective catalysts for the oxidation of alkylaromatic compounds, alcohols, and sulfides by hydrogen atom transfer (HAT) or S-oxidative processes has been described. Concerning the former systems, elucidation of mechanism and reactivity patterns of [(N4Py)FeII]2+ complex have been investigated in detail with respect to the generation of the iron-oxo and iron-peroxo active species both in common organic solvents and in non-common fluorinated solvents. For the N-hydroxyphthalimide catalyst, reactivity and selectivity patterns of the corresponding N-oxyl radical (PINO) in S-oxidation from sulfur compounds have been analysed by kinetic and product studies. In addition, the two systems can be used together in a mediated system, in which NHPI acts as efficient mediator in the oxidations of organic compounds promoted by the nonheme iron(IV)-oxo complex, enhancing its reactivity and expanding its oxidizing ability. In the mediated system, the increase of reactivity is associated to the oxidation of the mediator to the corresponding phthalimide-N-oxyl radical, which efficiently abstracts hydrogen atoms from the substrates regenerating the mediator NHPI. The possibility of a change of selectivity in the C-H functionalization of alkylaromatic compounds and alcohols has been studied in the presence of the NHPI mediator as a result of the different polar effects operating in the HAT processes promoted by [(N4Py)Fe(IV)=O]2+ and PINO radical. Furthermore, a change of chemoselectivity in the competitive oxidation of sulfides, alkylaromatic compounds and alcohols by effect of variation of the oxidizing species in the absence or in the presence of the NHPI mediator has been investigated.

Produzione scientifica

11573/1685374 - 2023 - Kinetic and Product Study of the S-oxidation vs HAT Chemoselectivity in Reactions Promoted by Nonheme Iron(IV)-oxo Complex/NHPI Mediator System
Di Berto Mancini, M.; Bernardini, M.; Emanuel Birzu, B.; De Santis, A.; Di Stefano, Stefano; Frateloreto, F.; Khaksar, D.; Lapi, A.; Olivo, G.; Lanzalunga, O. - 01a Articolo in rivista
rivista: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 1434-193X - wos: WOS:001031621400001 (0) - scopus: 2-s2.0-85164457925 (0)

11573/1684137 - 2023 - Oxidations of aromatic sulfides promoted by the phthalimide N-oxyl radical (PINO)
Di Berto Mancini, M.; Tabussi, A.; Bernardini, M.; Lanzalunga, O. - 01a Articolo in rivista
rivista: JOURNAL OF SULFUR CHEMISTRY (London : Taylor & Francis, 2004-) pp. 393-405 - issn: 1741-5993 - wos: WOS:000941862600001 (1) - scopus: 2-s2.0-85158850033 (1)

11573/1691319 - 2023 - Combining X-ray Absorption and NMR spectroscopies to investigate a chemical reaction in solution
Tavani, Francesco; Del Giudice, Daniele; Di Berto Mancini, Marika; Frateloreto, Federico; Busato, Matteo; Lanzalunga, Osvaldo; Di Stefano, Stefano; D’Angelo, Paola - 01a Articolo in rivista
rivista: RADIATION PHYSICS AND CHEMISTRY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 111199-1-111199-6 - issn: 0969-806X - wos: (0) - scopus: 2-s2.0-85168825418 (0)

11573/1603364 - 2022 - Two Faces of the Same Coin: Coupling X-Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes
Del Giudice, D.; Tavani, F.; Di Berto Mancini, M.; Frateloreto, F.; Busato, M.; Oliveira De Souza, D.; Cenesi, F.; Lanzalunga, O.; Di Stefano, Stefano; D'angelo, P. - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 0947-6539 - wos: WOS:000730219700001 (8) - scopus: 2-s2.0-85121358737 (6)

11573/1670870 - 2022 - Following a Silent Metal Ion: A Combined X-ray Absorption and Nuclear Magnetic Resonance Spectroscopic Study of the Zn2+ Cation Dissipative Translocation between Two Different Ligands
Frateloreto, Federico; Tavani, Francesco; Di Berto Mancini, Marika; Del Giudice, Daniele; Capocasa, Giorgio; Kieffer, Isabelle; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'angelo, Paola - 01a Articolo in rivista
rivista: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS (Washington, DC: American Chemical Society) pp. 5522-5529 - issn: 1948-7185 - wos: WOS:000819338000001 (7) - scopus: 2-s2.0-85133100528 (9)

11573/1582606 - 2021 - Change of Selectivity in C-H Functionalization Promoted by Nonheme Iron(IV)-oxo Complexes by the Effect of the N-hydroxyphthalimide HAT Mediator
Di Berto Mancini, M.; Del Gelsomino, A.; Di Stefano, Stefano; Frateloreto, F.; Lapi, A.; Lanzalunga, O.; Olivo, G.; Sajeva, S. - 01a Articolo in rivista
rivista: ACS OMEGA (Washington, D.C. : American Chemical Society, 2016-) pp. 26428-26438-26438 - issn: 2470-1343 - wos: WOS:000708560000051 (3) - scopus: 2-s2.0-85117484898 (5)

11573/1495076 - 2021 - Increasing the steric hindrance around the catalytic core of a self-assembled imine-based non-heme iron catalyst for C-H oxidation
Frateloreto, Federico; Capocasa, Giorgio; Olivo, Giorgio; Abdel Hady, Karm; Sappino, Carla; Di Berto Mancini, Marika; Levi Mortera, Stefano; Lanzalunga, Osvaldo; Di Stefano, Stefano - 01a Articolo in rivista
rivista: RSC ADVANCES (London: Royal Society of Chemistry) pp. 537-542 - issn: 2046-2069 - wos: WOS:000614277900058 (2) - scopus: 2-s2.0-85100382836 (2)

11573/1414508 - 2020 - Easy synthesis of a self-assembled imine-based iron(II) complex endowed with crown-ether receptors
Capocasa, G.; Di Berto Mancini, M.; Frateloreto, F.; Lanzalunga, O.; Olivo, G.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. 3390-3397 - issn: 1434-193X - wos: WOS:000537715700001 (5) - scopus: 2-s2.0-85086006273 (5)

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