{
  "abstract": "Modern organic synthesis aims to prepare the target molecule in a minimal number of steps. Hence, the efficiency, selectivity, and predictability of each of these steps need to be carefully optimized, even at a late stage of a synthetic route. This is particularly true in the case of aliphatic C-H functionalization, since differentiating one C-H bond among many others with similar properties in organic molecules often stands as an open challenge. Remote, inactivated C-H sites are especially difficult to target. Supramolecular catalysis represents one of the tools to overcome such problems. As occurs in enzymes, substrate binding to a supramolecular catalyst constrains their relative orientation, and the resulting preorganization can increase reactivity and unlock unusual selectivity in a rational and predictable manner, meeting late-stage functionalization requirements. In fact, supramolecular catalysis, which was initially oriented to the comprehension of the mechanisms of the involved reactions, is currently and rapidly evolving into a synthetically useful tool. One decade ago, in 2017, we described Fe- and Mn-based supramolecular catalysts equipped with crown ether recognition sites able to efficiently catalyze the oxidation of inactivated C-H bonds in protonated primary amines. Substrate preorganization induced by recognition enables elusive oxidation at remote C8 and C9 sites in linear alkyl chains. Since then, a number of follow-up investigations allowed us to rationally elicit unnatural reactivity and selectivity in different bioinspired oxidation reactions, including predictable, late-stage C-H oxidation of steroids. In addition, an in-depth analysis of such oxidation processes provides a deep comprehension of the action mechanism of these supramolecular catalysts. In this Account, we discuss the above investigations aiming to show (i) the rational approach to the design of a supramolecular oxidation catalyst, (ii) the experimental and theoretical tools that help understand and assess its mechanism of action, and (iii) its potential to address synthetic challenges. Eventually, a section that compares our approach to the one of other research groups illustrates the state of the art in supramolecular oxidation catalysis.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "name": "Giorgio Olivo"
    },
    {
      "name": "Miquel Costas"
    },
    {
      "name": "Stefano Di Stefano"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/54vkrsmk1w8a9.bib",
  "cited_by": 0,
  "doi": "10.1021/acs.accounts.6c00368",
  "fulltext_url": null,
  "id": "54vkrsmk1w8a9",
  "issns": [
    "0001-4842",
    "1520-4898"
  ],
  "landing_url": "https://hal.science/hal-05786768v1",
  "language": "en",
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "hal",
      "0.chim"
    ],
    [
      "openalex",
      "1604|Metal-Catalyzed Oxygenation Mechanisms"
    ]
  ],
  "openalex": "W7169866105",
  "pdf_url": "https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.6c00368?ref=article_openPDF",
  "pmcid": null,
  "pmid": null,
  "published": "2026-07-21",
  "publisher": "American Chemical Society",
  "ris": "https://research.draconitic.com/paper/54vkrsmk1w8a9.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:51Z",
      "native_id": "hal-05786768",
      "source": "hal",
      "url": "https://hal.science/hal-05786768v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Metal-Catalyzed Oxygenation Mechanisms",
      "subfield": "inorganic"
    }
  ],
  "title": "Rational Design of Supramolecular Fe and Mn Oxidation Catalysts",
  "title_text": "Rational Design of Supramolecular Fe and Mn Oxidation Catalysts",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:17:51Z",
  "url": "https://research.draconitic.com/paper/54vkrsmk1w8a9",
  "venue": "Accounts of Chemical Research",
  "versions": []
}