Enzyme-like Hydrogen Atom Transfer (HAT) Based Endo-Functionalized Molecular Receptors

Wenkai Pan; Anastasia Grigoryeva; Corrado Bacchiocchi; Pablo Ballester; Luca Valgimigli; Manuel Petroselli

doi:10.1021/acs.orglett.5c04339

Enzyme-like Hydrogen Atom Transfer (HAT) Based Endo-Functionalized Molecular Receptors

Org Lett. 2025 Dec 26;27(51):14201-14206. doi: 10.1021/acs.orglett.5c04339. Epub 2025 Dec 12.

Authors

Wenkai Pan¹, Anastasia Grigoryeva², Corrado Bacchiocchi³, Pablo Ballester^{4

5}, Luca Valgimigli^{1

2}, Manuel Petroselli^{4

6}

Affiliations

¹ University of Bologna, Department of Chemisty "G. Ciamician", Via Piero Gobetti 85, 40129 Bologna, Italy.
² Tecnopolo di Rimini, Via Dario Campana 71, 49722 Rimini, Italy.
³ University of Camerino, Chemistry Division, School of Science and Technology, Via Madonna delle Carceri, 62032 Camerino, Italy.
⁴ Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Av. Païs Catalans 16, 43007 Tarragona, Spain.
⁵ Catalans Institution for Research and Advanced Studies (ICREA), Passeig Luiś Companys 23, 08018 Barcelona, Spain.
⁶ University of Eastern Piedmont "Amedeo Avogadro", Department of Science and Technological Innovation, Viale Teresa Michel 11, 15121 Alessandria, Italy.

PMID: 41384678
DOI: 10.1021/acs.orglett.5c04339

Abstract

We report a series of endo-functionalized molecular receptors based on a calix[4]pyrrole scaffold, which exhibit Hydrogen Atom Transfer (HAT) reactivity towards free-radicals (e.g., peroxyl radicals). The chemical structure and shape of the molecular receptors affect the affinity towards free-radicals, while host-guest interactions are used to fine-tune the HAT reactivity, mimicking enzyme modulation in biological systems.