Research

Capriati’s main research revolves around:

(a)    Polar Organometallic Reagents in Stereoselective Organic Synthesis: Development and application of novel polar organometallic reagents, with a particular focus on functionalized organolithium species, and investigation of the structure-reactivity relationship of reactive lithiated intermediates using multinuclear magnetic resonance investigations, X-ray crystallography, and ab initio calculations (J. Org. Chem. 2008, 73, 9552; Chem. Eur. J. 2009, 15, 7958; Chem. Eur. J. 2010, 16, 9778; Chem. Eur. J. 2011, 17, 8216; Chem. Sci. 2014, 5, 528; Eur. J. Org. Chem. 2019, 5549). Contributions to key challenges in organometallic and lithium carbenoid chemistry, both in synthetic and mechanistic contexts. Notable advance include the direct functionalization of aryl-substituted oxygen-containing heterocycles (e.g., oxetanes, tetrahydrofurans and tetrahydropyrans) (Chem. Commun. 2011, 47, 9918; Chem. Commun. 2013, 49, 10160; Eur. J. Org. Chem. 2016, 3157), and the ortho-functionalization of aryloxetanes (Angew. Chem. Int. Ed. 2012, 51, 7532; Eur. J. Org. Chem. 2019, 5549); for reviews, see: Chem. Eur. J. 2010, 16, 4152; Dalton Trans. 2014, 43, 14204;

(b)    Mechanistic Insights into Deprotonative Metallation: Elucidation of how deprotonative metallation can be strategically leveraged in asymmetric synthesis to construct key building blocks en route to natural and bioactive compounds (Chem. Eur. J. 2009, 15, 7958; Chem. Commun. 2013, 49, 4911; Chem. Sci. 2014, 5, 528; Eur. J. Org. Chem. 2019, 5549);

(c)     Boron and Fluorine chemistry in Supramolecular Assembly: Exploration of weak, non-covalent inter- and intramolecular interactions that drive the formation of supramolecular architectures via spontaneous self-assembly processes (Chem. Eur. J. 2010, 16, 9778; Dalton Trans. 2015, 44, 19447);

(d)    Deep Eutectic Solvents (DESs) as Green Reaction Media: Pioneering the use of DESs as sustainable, biodegradable alternatives to toxic VOCs in various chemical transformations, including: (a) organocatalysis (Green Chem. 2016, 18, 792; Beilstein J. Org. Chem. 2016, 12, 2620); (b) whole cells biocatalysis (Adv. Synth. Cat. 2017, 359, 1049; Catalysts 2018, 8, 55; React. Chem. Eng. 2020, 5, 859); (c) metal-catalysis also integrated with biocatalysis (Green Chem. 2017, 19, 69; Green Chem. 2018, 20, 3468; ChemSusChem 2018, 11, 3495; Front. Chem. 2019, 7, 723; ChemCatChem 2020, 12, 1979; Org. Biom. Chem. 2021, 19, 1773; ChemSusChem 2022, 15, e202102211; RSC Sustain. 2023, 1, 847; EurJOC 2024, e202400300; ChemCatChem 2025, 17, e01019); (d) aminocarbonylation reactions (Chem. Commun. 2018, 54, 8100); (e) as electrolyte components in dye-sensitized solar cells (Energy Technol. 2017, 5, 345; Chem. Eur. J. 2018, 24, 17656; ChemElettroChem 2020, 7, 1707; Sustain. Energy Fuels 2024, 8, 504); (f) synthesis of (chiral) amines and heterocycles of pharmaceutical interests (ChemSusChem 2020, 13, 358; Molecules 2022, 27, 7594; ACS Sustainable Chem. Eng. 2022, 10, 4065; Molecules 2024, 29, 1399; ChemSusChem 2025, DOI: 10.1002/cssc.202502114); (g) electrochemistry (Solid State Ionics 2018, 323, 48); (h) biotechnological applications with photosynthetic bacteria (ACS Sust. Chem. Eng. 2017, 5, 7768); (i) chemistry of graphene (Sci. Rep. 2019, 9, 5463); (j) synthesis of heterocycles (Tetrahedron 2016, 72, 4239; Molecules 2016, 21, 924; Eur. J. Org. Chem. 2019, 5549; Molecules 2020, 25, 574; Beilstein J. Org. Chem. 2020, 16, 1915; Eur. J. Org. Chem. 2022, e202200843; Eur. J. Org. Chem. 2023, 26, e202200814); (k) extractive processes of mycotoxins (Molecules 2017, 22, 121); and (l) protein crystallization (ACS Sustainable Chem. Eng. 2021, 9, 8435);

(e)    Organometallic Chemistry in Aqueous and Eutectic Environments: Challenging the long-standing paradigm that highly polarized organometallic compounds require strict anhydrous conditions, Capriati’s research team has reported that highly reactive organometallic compounds of s-block elements (organolithium, organomagnesium, and organosodium reagents) can be employed in protic eutectic mixtures or even in water under aerobic ambient conditions, with applications in: (a) in nucleophilic additions to carbonyl derivatives, imines, nitriles, Weinreb amides, and acyl substitutions (Chem. Sci. 2016, 7, 1992; Green Chem. 2017, 19, 3069; Angew. Chem. Int. Ed. 2017, 56, 1020; Angew. Chem. Int. Ed. 2023, e202304720); (b) ortho- and lateral-lithiation and nucleophilic acyl substitution reactions in benzamide derivatives (Chem. Commun. 2014, 50, 8655; Chem. Commun. 2015, 51, 9459; Chem. Commun. 2019, 55, 7741); (c) enolate chemistry (React. Chem. Eng. 2021, 6, 1796; Org. Biom. Chem. 2024, 22, 1885); (d) direct Pd-catalyzed cross-coupling reactions with aryl halides in water (Angew. Chem. Int. Ed. 2019, 58, 1799); and (e) ultrafast Negishi cross-coupling reactions in DESs and water (Angew. Chem. Int. Ed. 2021, 60, 10632); for recent reviews, see: Eur. J. Org. Chem. 2015, 31, 6778; Chem. Eur. J. 2018, 24, 14854; Curr. Opin. Green Sust. Chem. 2021, 30, 100487; Molecules 2024, 29, 1422. These discoveries redefine the fundamental understanding of organometallic reactivity and open new avenues for sustainable synthetic methodologies.

SELECTED PUBLICATIONS:

  • Delvecchio, L. Cicco, A. Paparella, G. Di Salvo, F. M. Perna, V. Capriati “A Scalable and Sustainable Synthesis of Indirubin Frameworks Enabled by Deep Eutectic Solvents”
      ChemSusChem 2025, accepted; DOI: 10.1002/cssc.202502114
    1. G. Dilauro, C. Luccarelli, A. F. Quivelli, A.Vitale, F. M. Perna, V. Capriati “Introducing Water and Deep Eutectic Solvents in Organosodium Chemistry: Chemoselective Nucleophilic Functionalizations in Air" Angewandte Chemie International Edition 2023, e202304720 (selected by the Editorial Office as Hot Paper)
    2. G. Dilauro, L. Cicco, P. Vitale, F. M. Perna, V. Capriati “Ligand-Free Pd-Catalyzed Reductive Mizoroki-Heck Reaction Strategy for the One-Pot Synthesis of Functionalized Oxygen Heterocycles in Deep Eutectic Solvents” European Journal of Organic Chemistry 2023, e202200814 (selected by the Editorial Office as Very Important Paper and for the Front Cover of the corresponding issue)
    3. A. F. Quivelli, M. Marinò, P. Vitale, J. García-Álvarez, F. M. Perna, Vito Capriati “Ligand-free Copper-Catalyzed Ullmann-type C–O Bond Formation in Non-innocent Deep Eutectic Solvents under Aerobic Conditions” ChemSusChem 2022, 15, e202102211
    4. G. Dilauro, C. S. Azzolini, P. Vitale, A. Salomone, F. M. Perna, V. Capriati “Scalable Negishi Coupling between Organozinc Compounds and (Hetero)Aryl Bromides under Aerobic Conditions when using Bulk Water or Deep Eutectic Solvents with no Additional Ligands” Angewandte Chemie International Edition 2021, 60, 10632 (this article appears in: Hot Topic: C-C Coupling, ChemCatChem)
    5. L. Cicco, A. Fombona-Pascual, A. Sánchez-Condado, G. A. Carriedo, F. M. Perna, V. Capriati, A. Presa Soto, J. García-Álvarez “Fast and Chemoselective Addition of Highly Polarized Lithium Phosphides Generated in Deep Eutectic Solvents to Aldehydes and Epoxides” ChemSusChem 2020, 13, 4967 (selected by the Editorial Office as Very Important Paper and for the Cover Feature of the corresponding issue; Highlighted in ChemistryViews)
    6. L. Cicco, A. Salomone, P. Vitale, N. Ríos-Lombardía, J. González-Sabín. J. García-Álvarez, F. M. Perna, V. Capriati “Addition of Highly Polarized Organometallic Compounds to N-tert-Butanesulfinyl Imines in Deep Eutectic Solvents under Air: Preparation of Chiral Amines of Pharmaceutical Interest” ChemSusChem 2020, 13, 3583 (selected by the Editorial Office for the Cover Feature of the corresponding issue)
    7. G. Dilauro, A. F. Quivelli, P. Vitale, V. Capriati, F. M. Perna “Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd-Catalysed Cross-Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides” Angewandte Chemie International Edition 2019, 58, 1799 (selected by the Editorial Office as Hot Paper; Top Downloaded Paper 2018–2019)
    8. G. Dilauro, S. M. García, D. Tagarelli, P. Vitale, F. M. Perna, V. Capriati “Ligand-Free Bioinspired Suzuki–Miyaura Coupling Reactions using Aryltrifluoroborates as Effective Partners in Deep Eutectic Solvents” ChemSusChem 2018, 11, 3495 
    9. G. Dilauro, M. Dell’Aera, P. Vitale, V. Capriati, F. M. Perna “Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Noninnocent Reaction Medium” Angewandte Chemie International Edition 2017, 56, 10200 (HIGHLIGHTED in Synfacts 2017, 13 (10), 1074 and in ChemistryViews)
    10. L. Cicco, S. Sblendorio, R. Mansueto, F. M. Perna, A. Salomone, S. Florio, V. Capriati “Water Opens the Door to Organolithiums and Grignard Reagents: Exploring and Comparing the Reactivity of Highly Polar Organometallic Compounds in Unconventional Reaction Media Towards the Synthesis of Tetrahydrofurans" Chemical Science 2016, 7, 1192 (HIGHLIGHTED in Synfacts 2016, 12 (1), 0081)
    11. A. Salomone, F. M. Perna, A. Falcicchio, S. O. Nilsson Lill, A. Moliterni, R. Michel, S. Florio, D. Stalke, V. Capriati “Direct Observation of a Lithiated Oxirane: A Synergistic Study Using Spectroscopic, Crystallographic, and Theoretical Methods on the Structure and Stereodynamics of Lithiated ortho-Trifluoromethyl Styrene Oxide” Chemical Science 2014, 5, 528 (selected by the Chemical Science Editorial Office as Hot Paper)

    pubblicato il 06/06/2013 — ultima modifica 06/12/2025

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