{
  "abstract": "N-Heterocyclic arynes are versatile but underutilized intermediates for rapidly functionalizing N-containing arenes. Part of the reason for the underutilization of N-heterocyclic arynes is that 5-membered N-heterocyclic arynes are inaccessible due to ring strain. In 2024, our group demonstrated that coordinating such strained intermediates to a metal center could stabilize the aryne bond via metal back-donation and thereby enable formation of otherwise inaccessible 5-membered heterocyclic arynes. Interestingly, heterocycles such as 4-azaindole and benzofuran that lacked subtle steric interactions were found to form borate complexes instead of the desired aryne during the key transmetallation step. Herein, we employ a computationally guided ligand approach to overcome this borate complex formation to generate the desired arynes. Using our computational findings, we accessed new previously inaccessible arynes: 4-azaindol-2,3-yne, pyrrolo-2,3-yne pyrazine, and the first ever proposed aryne, benzofuran-2,3-yne, all bound to Ni. Additionally, we report on a novel 5-membered aryne mode of reactivity in the form of a formal inverse-demand Diels–Alder reaction to yield a new class of underexplored heterocycles.",
  "abstract_shown": true,
  "affiliations": [
    "University of Minnesota, Department of Chemistry Minneapolis MN 55455 USA",
    "Oberlin College, Department of Chemistry and Biochemistry Oberlin Ohio 44074 USA"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Sanu Siyad Pullarat"
    },
    {
      "affs": [
        0
      ],
      "name": "Ali A. Younis"
    },
    {
      "affs": [
        1
      ],
      "name": "Gabriel N. Morais",
      "orcid": "0000-0003-2439-8861"
    },
    {
      "affs": [
        0
      ],
      "name": "Matthew C. Fitzsimmons"
    },
    {
      "affs": [
        0
      ],
      "name": "Roman G. Belli"
    },
    {
      "affs": [
        0
      ],
      "name": "Jenna N. Humke"
    },
    {
      "affs": [
        1
      ],
      "name": "Shuming Chen",
      "orcid": "0000-0003-1897-2249"
    },
    {
      "affs": [
        0
      ],
      "name": "Courtney C. Roberts",
      "orcid": "0000-0001-8177-4013"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/56wwqdqh9m5ss.bib",
  "cited_by": 0,
  "doi": "10.1039/d6sc05533h",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13573234/",
  "id": "56wwqdqh9m5ss",
  "issns": [
    "2041-6520",
    "2041-6539"
  ],
  "landing_url": "https://doi.org/10.1039/d6sc05533h",
  "language": "en",
  "licence": "CC-BY-NC-3.0",
  "licence_label": "CC BY-NC 3.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc/3.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Chemistry"
    ],
    [
      "openalex",
      "1605|Cyclization and Aryne Chemistry"
    ]
  ],
  "openalex": "W7213195730",
  "pdf_url": null,
  "pmcid": "PMC13573234",
  "pmid": "42741599",
  "published": "2026-09-14",
  "publisher": "Royal Society of Chemistry",
  "ris": "https://research.draconitic.com/paper/56wwqdqh9m5ss.ris",
  "sources": [
    {
      "first_seen": "2026-11-07T12:23:28Z",
      "native_id": "PMC13573234",
      "source": "pmc",
      "url": "https://doi.org/10.1039/d6sc05533h"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Cyclization and Aryne Chemistry",
      "subfield": "organic"
    }
  ],
  "title": "Access to and unexplored reactivity of nickel-bound 5-membered O- and N-heterocyclic arynes via computational insight",
  "title_text": "Access to and unexplored reactivity of nickel-bound 5-membered O- and N-heterocyclic arynes via computational insight",
  "type": "peer-reviewed",
  "updated_at": "2026-11-08T12:20:58Z",
  "url": "https://research.draconitic.com/paper/56wwqdqh9m5ss",
  "venue": "Chemical Science",
  "versions": []
}