{
  "abstract": "The development of Shono-type oxidation reactions for late-stage functionalization has recently focused on the expansion of compatible nucleophiles; however, a central limitation is N-aryl, or aniline-derived, substrates due to oxidative sensitivity that leads to decomposition under direct electrolysis. Redox mediators have recently been employed to drive Shono-type oxidation reactions at lower overpotentials but are underdeveloped with aniline-type substrates. We demonstrate that electron-transfer (ET)-based ferrocene (Fc) mediators are capable of driving a rare Shono-type allylation reaction using simple allyl trifluoroborate salt with a variety of N-aryl substrates. Computational data probing the nature of ET from substrate to Fc+ suggests a distinct π-interaction, leading to our evaluation of phenyl-appended Fc (FcPh) for enhanced reactivity. We find that FcPh improves reaction efficiency across structurally diverse N-aryl substrates under controlled potential electrolysis (CPE) at applied potentials differing only by 20 mV, illustrating a distinct handle for tuning Fc redox mediators via proposed non-covalent interactions. DFT supports a working model for “out-ofcage” and “in-cage” single electron transfer (SET)pathways that provides a rationale for observed trends. In the presence of benzene co-solvent, the advantage of FcPh is suppressed, supporting the proposed role of π-interactions between FcPh and N-aryl substrates. These results highlight mediatorbased π-interactions as a strategy for tuning mediation efficiency without substantial alteration of mediator redox potential.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "Boston University",
    "Department of Chemistry and Biochemistry",
    "University of California"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Yahui Guo"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Siyuan Su"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Lupita S. Ramirez"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "XiaoAn Wu"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Osvaldo Gutierrez"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Joseph Derosa",
      "orcid": "0000-0001-8672-4875"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/fwb3897sxr488.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008696/v1",
  "fulltext_url": null,
  "id": "fwb3897sxr488",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008696/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Radical Photochemical Reactions"
    ]
  ],
  "openalex": "W7212250887",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008696/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-11",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/fwb3897sxr488.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008696",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008696/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Radical Photochemical Reactions",
      "subfield": "organic"
    }
  ],
  "title": "π-Interaction-Guided Tuning of Ferrocene Redox Mediators for Shono-Type Allylation of N-Aryl Amines",
  "title_text": "π-Interaction-Guided Tuning of Ferrocene Redox Mediators for Shono-Type Allylation of N-Aryl Amines",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/fwb3897sxr488",
  "venue": "ChemRxiv",
  "versions": []
}