{
  "abstract": "4-Phenyl-1,2,4-triazoline-3,5-dione (PTAD) is known as the most reactive commercially available dienophile, as it rapidly reacts with dienes at low temperatures and high dilution. In general terms, PTAD is a very soft Lewis acid, with a strong affinity towards electron rich alkenes. In this work, we report that the potent π-acid PTAD also shows a very useful and general σ-acid reactivity towards electron rich C(sp3)-H bonds, opening up its use in alkane amination reactions, as well as in late stage functionalization applications. The experimental observations over a wide range of alkanes, as well as in more functionalized substrates, indicate a carbocationic mechanism involving a hydride ion transfer of the alkane substrate to PTAD. The carbocation is very transient, as C-N bond formation proceeds generally with retention of the original configuration of a stereogenic carbon. The reaction can be run at high conversion of the alkane substrate using a catalytic amount of a gold(I)-catalyst combined with a mild proton donor such as hexafluoroisopropanol (HFIP). The reaction can often fully discriminate between very similar C-H bonds, such as cyclic alkanes over linear ones, equatorial C-H bonds over axial ones and tertiary over secondary ones. These observed reactivity orders closely follow expected trends in carbocation stability, offering a conveniently predictability. This novel C-H functionalization method does not require extensive catalyst or reagent design and offers good complementary to more conventional C-H activation or amination methodologies.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 5,
  "authors": [
    {
      "name": "Daniel Uherek"
    },
    {
      "name": "Marios Kidonakis"
    },
    {
      "name": "Kevin Bevernaege"
    },
    {
      "name": "Kristof Van Hecke"
    },
    {
      "name": "Johan Maurits Winne",
      "orcid": "0000-0002-9015-4497"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/dwq9x5b3n385w.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010490/v1",
  "fulltext_url": null,
  "id": "dwq9x5b3n385w",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010490/v1",
  "language": null,
  "licence": "CC-BY-NC",
  "licence_label": "CC BY-NC",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Catalytic C–H Functionalization Methods"
    ]
  ],
  "openalex": "W7222219279",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-15",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/dwq9x5b3n385w.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010490",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010490/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic C–H Functionalization Methods",
      "subfield": "organic"
    }
  ],
  "title": "Directing group-free site-selective and stereoretentive C-H amination of alkanes with phenyl triazolinedione (PTAD) as a σ-acid",
  "title_text": "Directing group-free site-selective and stereoretentive C-H amination of alkanes with phenyl triazolinedione (PTAD) as a σ-acid",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/dwq9x5b3n385w",
  "venue": "ChemRxiv",
  "versions": []
}