Research

Capriati’s main research revolves around:

(a) the design and application in stereoselective organic synthesis of novel polar organometallic reagents with special emphasis on functionalised organolithium species, and the elucidation of the structure-reactivity relationship of reactive lithiated intermediates by combining multinuclear magnetic resonance investigations with X-ray data 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). His work has contributed to paving the way towards key challenges in the area of organometallic and lithium carbenoid chemistry (both synthetic and mechanistic aspects) (for reviews: Chem. Eur. J. 2010, 16, 4152; Dalton Trans. 2014, 43, 14204). Recent breakthroughs include (a) the employment of organometallics with applications in the direct functionalisation 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-functionalisation of aryloxetanes (Angew. Chem. Int. Ed. 2012, 51, 7532; Eur. J. Org. Chem. 2019, 5549);

(b) informative mechanistic studies codifying how deprotonative metallation can be successfully exploited in the asymmetric synthesis of key buiding 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) novel developments in boron and fluorine chemistry with a particular focus on the role played by weak, non-covalent inter- and intramolecular interactions in promoting the formation of supramolecular motifs through spontaneous self-assembly processes (Chem. Eur. J. 2010, 16, 9778; Dalton Trans. 2015, 44, 19447);

(d) the investigation of Deep Eutectic Solvents (DESs) as a new generation of promising green and unconventional reaction media, in replacing traditional and toxic VOCs, for the development of a sustainable chemistry in organocatalysis (Green Chem. 2016, 18, 792; Beilstein J. Org. Chem. 2016, 12, 2620), in whole cells biocatalysis (Adv. Synth. Cat. 2017, 359, 1049; Catalysts 2018, 8, 55; React. Chem. Eng. 2020, 5, 859), in metal-catalysis also interfaced 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), in aminocarbonylation reactions (Chem. Commun. 2018, 54, 8100), as electrolyte components in a new generation of dye-sensitized solar cells (Energy Tech. 2017, 5, 345; Chem. Eur. J. 2018, 24, 17656; ChemElettroChem 2020, 7, 1707), in the preparation of chiral amines of pharmaceutical interests (ChemSusChem 2020, 13, 358), in electrochemistry (Solid State Ionics 2018, 323, 48), in biotechnological applications with photosynthetic bacteria (ACS Sust. Chem. Eng. 2017, 5, 7768), in the chemistry of graphene (Sci. Rep. 2019, 9, 5463), in the 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), and in extractive processes of mycotoxins (Molecules 2017, 22, 121).

It has always been a firm conviction of the scientific community that the employment of both anhydrous conditions and water-free reaction media is required for the successful handling of highly polarized organometallic compounds of s-block elements because of their high reactivity. Capriati’s research team has reported the breakthrough discoveries that organolithium reagents can be successfully used, employing either protic eutectic mixtures or water as reaction medium, under batch conditions, at room temperature and under air (a) in nucleophilic additions to carbonyl derivatives, imines and nitriles (Chem. Sci. 2016, 7, 1992; Green Chem. 2017, 19, 3069; Angew. Chem. Int. Ed. 2017, 56, 1020), (b) in ortho- and lateral-lithiation reactions and in nucleophilic acyl substitution reactions in benzamide derivatives (Chem. Commun. 2014, 50, 8655; Chem. Commun. 2015, 51, 9459; Chem. Commun. 2019, 55, 7741) and (c) in direct Pd-catalysed cross-coupling reactions with aryl halides (Angew. Chem. Int. Ed. 2019, 58, 1799). Pd-catalysed Negishi couplings between (functionalised) organozinc halides and (hetero)aryl bromides have also been successfully performed both in DESs and in water, under mild and aerobic conditions, and in short reaction times (20 s) (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).

SELECTED PUBLICATIONS

F. Quivelli, F. V. Rossi, P. Vitale, J. García-Álvarez, F. M. Perna, V. Capriati “Sustainable and Scalable Two-Step Synthesis of Thenfadil and Some Analogs in Deep Eutectic Solvents: From Laboratory to Industry” ACS Sustainable Chemistry & Engineering 2022, 10, 4065–4072 (selected by the Editorial Office for the Front Cover of the corresponding issue)
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
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 2022, e202200814 (selected by the Editorial Office as Very Important Paper and for the Front Cover of the corresponding issue)
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; Angewandte Chemie 2021, 133, 10726 (this article also appears in: Hot Topic: C-C Coupling, ChemCatChem)
L. Cicco, A. Fombona-Pascual, A. Sánchez-Condado, Gabino A. Carriedo, Filippo Maria Perna, Vito Capriati, Alejandro Presa Soto, Joaquín 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: https://www.chemistryviews.org/details/ezine/11264622/Highly_Reactive_Lithium_Phosphides_Tamed_in_Deep_Eutectic_Solvents.html).
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).
P. Vitale, F. Lavolpe, F. Valerio, M. Di Biase, F. M. Perna, E. Messina, G. Agrimi, I. Pisano, V. Capriati “Sustainable chemo-enzymatic preparation of enantiopure (R)-β-hydroxy-1,2,3-triazoles via lactic acid bacteria-mediated bioreduction of aromatic ketones and a heterogeneous “click” cycloaddition reaction in deep eutectic solvents”, React. Chem. Eng. 2020, 5, 859.
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; Angewandte Chemie 2019, 131, 1813 (selected by the Editorial Office as Hot Paper; Top Downloaded Paper 2018–2019).
S. Ghinato, G. Dilauro, F. M. Perna, V. Capriati, M. Blangetti, C. Prandi “Directed ortho-Metalation–Nucleophilic Acyl Substitution Strategies in Deep Eutectic Solvents: The Organolithium Dictates the Chemoselectivity”, Chemical Communication 2019, 55, 7741; HIGHLIGHTED in Synfacts 2019, 15 (09) 1020 (selected by the Editorial Office for the Front Cover of the corresponding issue).
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.
J. García-Álvarez, E. Hevia, V. Capriati “The Future of Polar Organometallic Chemistry Written in Bio-based Solvents and Water”, Chemistry – A European Journal 2018, 24, 14854 (selected by the Editorial Office for the section "Hot Collection: Sustainable Chemistry" and for their Showcase of outstanding Review-type articles ).
L. Cicco, N. Ríos-Lombardía, M. J. Rodríguez-Álvarez, F. Morís, F. M. Perna, V. Capriati, J. García-Álvarez, J. González-Sabín “Programming Cascade Reactions Interfacing Biocatalysis with Transition-metal Catalysis in Deep Eutectic Solvents as Biorenewable Reaction Media”, Green Chemistry 2018, 20, 3468 (selected by the Editorial Office for the Inside Front Cover of the corresponding issue and as HOT Paper).
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; Angewandte Chemie 2017, 129, 10334 (HIGHLIGHTED in Synfacts 2017, 13 (10), 1074 and in ChemistryViews: https://www.chemistryviews.org/details/ezine/10603789/Water_Tames_Grignard_and_Organolithium_Reagents.html).
L. Cicco, M. J. Rodríguez-Álvarez, F. M. Perna, J. García-Álvarez, V. Capriati “One-pot Sustainable Synthesis of Tertiary Alcohols by Combining Ruthenium-catalyzed Isomerization of Allylic Alcohols and Chemoselective Addition of Polar Organometallic Reagents in Deep Eutectic Solvents”, Green Chemistry 2017, 19, 3069.
P. Vitale, V. M. Abbinante, F. M. Perna, A, Salomone, C. Cardellicchio, V. Capriati “Unveiling the Hidden Performance of Whole Cells in the Asymmetric Bioreduction of Aryl-containing Ketones in Aqueous Deep Eutectic Solvents”, Advanced Synthesis & Catalysis 2017, 359, 1049.
E. Massolo, S. Palmieri, M. Benaglia, V. Capriati, F. M. Perna “Stereoselective Organocatalysed Reactions in Deep Eutectic Solvents: Highly Tunable and Biorenewable Reaction Media for Sustainable Organic Synthesis”, Green Chemistry 2016, 18, 792.
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.
J. García-Álvarez, E. Hevia, V. Capriati “Reactivity of Polar Organometallic Compounds in Unconventional Reaction Media: Challenges and Opportunities”, European Journal of Organic Chemistry 2015, 31, 6779.
V. Mallardo, R. Rizzi, F. C. Sassone, R. Mansueto, F. M. Perna, A. Salomone, V. Capriati “Regioselective Desymmetrization of Diaryltetrahydrofurans via Directed ortho-Lithiation: An Unexpected Help from Green Chemistry”, Chemical Communications 2014, 50, 8655.
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) .
D. I. Coppi, A. Salomone, F. M. Perna, V. Capriati “Exploiting the Lithiation-Directing Ability of Oxetane for the Regioselective Preparation of Functionalized 2-Aryloxetane Scaffolds under Mild Conditions”, Angewandte Chemie International Edition 2012, 51, 7532–7536; Angewandte Chemie 2012, 124, 7650; HIGHLIGHTED in Synfact 2012, 8 (11), 1247.