{
  "abstract": "The Cu I -triazolide intermediate of the Cu-mediated alkyne-azide cycloaddition (CuAAC) typically undergoes rapid proto-demetallation but can be intercepted by suitable coupling partners to give 5-substituted triazole products. However, the scope of such “interrupted click” reactions is restricted because some partners react too slowly to outcompete proto-demetallation or even actively promote the decomposition of the Cu I -triazolide in preference to the desired coupling. Here we show that mechanical stabilisation of a Cu I -triazolide within a [2]rotaxane can allow otherwise unproductive “hidden” interrupted click reactions to proceed; the triazolide intermediate of the active template CuAAC reaction couples with cyanide and primary amines under oxidative conditions to install these groups at the triazole 5-position in up to 99% yield. In contrast, the interlocked triazolide reacts slowly with some typical interrupted electrophiles that intercept non-interlocked Cu I -triazolides. Based on these reactivity trends, we propose that the mechanical bond prevents direct attack of electrophiles on the Cu-C bond, instead enforcing inner-sphere reactivity at the Cu I centre with a Cu I /Cu III /Cu I redox cycle. The C-5 substituent leads to a new source of mechanical positional isomerism and a suitably designed macrocycle can be removed after the coupling, allowing the interlocked architecture to serve as an auxiliary for products of otherwise inaccessible interrupted click reactions.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, Teknikringen 30, Stockholm, Sweden, 10044",
    "Department of Chemistry, University of Warwick, Gibbet Hill Rd, Coventry, UK, CV4 7AL",
    "School of Chemistry",
    "University of Birmingham",
    "Department of Chemistry",
    "Stockholm University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Anja Ramström"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Qilong Sun"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Daisy R. S. Pooler"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "A. Ken Inge"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Stephen M. Goldup"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Fredrik Schaufelberger",
      "orcid": "0000-0001-5298-4310"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/fgq6he5tqnsxz.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010334/v1",
  "fulltext_url": null,
  "id": "fgq6he5tqnsxz",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010334/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|Click Chemistry and Applications"
    ]
  ],
  "openalex": "W7221613317",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010334/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-13",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/fgq6he5tqnsxz.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010334",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010334/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Click Chemistry and Applications",
      "subfield": "organic"
    }
  ],
  "title": "The Mechanical Bond Reveals Hidden Interrupted Click Reactions",
  "title_text": "The Mechanical Bond Reveals Hidden Interrupted Click Reactions",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/fgq6he5tqnsxz",
  "venue": "ChemRxiv",
  "versions": []
}