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E. Spatola, R. Cacciapaglia, F. Frateloreto, A. Procopio, F. Giannetti, L. Napoli, M. De Angelis, S. Di Stefano, G. Olivo, Organic Letters, 2025, 27, 6605−6610 ..
Challenging cyclization of common- to medium-sized rings are promoted by nanoconfinement inside the cavity of a self-assembled hexameric resorcinarene capsule. While no cyclization occurs outside the capsule, high to excellent yields of cycloalkane-[b]-indoles are obtained inside the capsule irrespective of ring size (5-8 members). Kinetic analysis coupled to NMR investigation of substrate binding shows that the cyclization step under nanoconfinement is not rate-determining, not even for the formation of an 8-membered ring .
A. Fagnano, G. Capocasa, F. Frateloreto, L. Latini, S. Levi Mortera, O. Lanzalunga, S. Di Stefano, G. Olivo, Chem. Eur. J. 2025, 31, e202404041.
Understanding how modification of receptor position and orientation in a supramolecular catalyst affects its efficiency is key for rational catalyst design but still underexplored. Herein, we quantified the impact of different receptor orientations on the C-H oxidation efficiency by supramolecular Fe(IV)=O complexes. Overall, their efficiency is similar but some changes in the selectivity profile are observed.
A. Fagnano, F. Frateloreto, R. Paoloni, C. Sappino, O. Lanzalunga, M. Costas, S. Di Stefano, G. Olivo, Angewandte Chemie International Edition, 2024, e202401694, (HOT ARTICLE).
We report evidence that supramolecular substrate binding increases several aspects of iron (IV) oxo (Fe(IV)=O) reactivity not only in nonheme oxygenases but also in synthetic models. Recognition-induced proximity of certain substrate C-H bonds increases both rate and selectivity for their C-H abstraction, analyzed by Effective Molarity, and increases the efficiency of subsequent Oxygen Rebound, as exclusively observed in enzymes.
E. Spatola, F. Frateloreto, D. Del Giudice, G. Olivo, S. Di Stefano, Current Opinion in Colloid & Interface Science, 2023, 64, 101680.
This review focuses on cyclization reactions occurring in nano-sized confined spaces. It is shown that such approach allows to improve cyclizations in terms of yields, reaction rates and product distributions.
G. Olivo, G. Capocasa, D. Del Giudice, O. Lanzalunga,, S. Di Stefano, Chemical Society Reviews, 2021, 50, 7681–7724. (TOP 5% of highly cited works from the Royal Society of Chemistry Journals)
Recent advancements in supramolecular catalysis are reviewed, which show the high potential of related tools when applied to organic synthesis. Nanoconfinement of reactants, recognition driven and processive catalysis, regulation of catalysis by molecular machines are recognized as innovative instruments that can pave the way to alternative synthetic strategies.
G. Olivo, G. Capocasa, B. Ticconi, O. Lanzalunga, S. Di Stefano, M. Costas, Angewandte Chemie International Edition, 2020, 59, 12703 –12708 (VIP ARTICLE).
Analysis of substrate binding mode to a supramolecular catalyst enables rational prediction of site-selectivity in late-stage C(sp3)-H oxidation of aminosteroids.
G. Capocasa, F. Sessa, F. Tavani, M. Monte, G. Olivo, S. Pascarelli, O. Lanzalunga, S. Di Stefano, P. D’Angelo, Journal of The American Chemical Society, 2019, 141, 2299−2304.
G. Olivo, G. Capocasa, O. Lanzalunga, S. Di Stefano, M. Costas, Chemical Communication, 2019, 55, 917-920.
Substrate-selectivity stemming from recognition is a key feature of enzymes that has been seldom observed in artificial catalysts. Herein, we report a recognition-driven, substrate-selective C–H oxidation that inverts the intrinsic reactivity of the competing C–H bonds. Analysis of this selectivity highlights an unexpectedly high reactivity enhancement imparted by intramolecularity.
G. Olivo, G. Farinelli, A. Barbieri, O. Lanzalunga, S. Di Stefano, M. Costas, Angewandte Chemie International Edition 2017, 56, 16347 –16351
Supramolecular recognition of protonated primary amines on 18-crown-6 receptors exposes specific, remote methylenes to the Mn active site. Linear alkyl chains can thus be selectively oxidized on C8 and C9 positions with H2O2, overriding the intrinsic reactivity of C-H bonds.
G. Capocasa, G. Olivo, A. Barbieri, O. Lanzalunga, S. Di Stefano, Catalysis Science & Technology 2017 , 7, 5677–5686. (HOT ARTICLE)
An imine-based catalyst easily obtained by self assembly of cheap and commercially available starting materials, selectively catalyzes the hydroxylation of aromatic compounds.
G. Olivo, A. Barbieri, V. Dantignana, F. Sessa, V. Migliorati, M. Monte, S. Pascarelli, T. Narayanan, O. Lanzalunga, S. Di Stefano, P. D’Angelo, Journal of Physical Chemistry Letters 2017, 8, 2958−2963.
G. Olivo, O. Lanzalunga, S. Di Stefano, Advanced Synthesis & Catalysis, 2016, 358, 843−863.
G. Olivo, M. Nardi, D. Vìdal-Sanchez, A. Barbieri, A. Lapi, L. Gómez, O. Lanzalunga, M. Costas, S. Di Stefano, Inorganic Chemistry 2015, 54, 10141–10152.
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