{
  "abstract": "Inert aliphatic C–O bonds are ubiquitous in both natural and synthetic feedstocks, yet their direct functionalization remains a formidable challenge in sustainable synthesis. Here we report a tandem strategy that merges thermal zirconium-mediated deoxygenation of alkenyl ethers with visible-light-induced nickel-catalyzed cross-coupling. Through β-oxygen elimination and chain walking, readily available ethers are transformed into alkylzirconocene nucleophiles, enabling efficient C(sp3)–C(sp3) and C(sp3)–C(sp2) bond formation with alkyl and aryl iodides. The method exhibits broad functional group tolerance, late-stage applicability to pharmaceuticals and natural products, gram-scale scalability, and an enantioselective variant (94% ee). Notably, the oxygen-retentive reaction of dihydropyran and the dual functionalization of PMB-protected ethers highlight the atom-economical potential of this protocol. Mechanistic studies elucidate the preference for β-oxygen elimination over β-hydride elimination and reveal the role of a special Zr (III) species as a single-electron donor in the catalytic cycle. This work provides a direct route from unactivated aliphatic C–O bonds to functionalized alkanes, advancing the sustainable valorization of renewable biomass feedstocks.",
  "abstract_shown": true,
  "affiliations": [
    "School of Life Sciences",
    "Tsinghua University",
    "National Institute of Biological Sciences, Zhongguancun Life Science Park, Beijing, China, 102206",
    "Tsinghua Institute of Multidisciplinary Biomedical Research, Tsinghua University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Haowen Xu",
      "orcid": "0009-0009-8344-2990"
    },
    {
      "affs": [
        2
      ],
      "name": "Songlin Bai"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Bin Yang"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Yijie Huang"
    },
    {
      "affs": [
        2
      ],
      "name": "Gen Li"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Xiangbing Qi"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/6k6vb5k3vvejp.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008196/v1",
  "fulltext_url": null,
  "id": "6k6vb5k3vvejp",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008196/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Catalytic Cross-Coupling Reactions"
    ]
  ],
  "openalex": "W7205008532",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008196/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-02",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/6k6vb5k3vvejp.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008196",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008196/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic Cross-Coupling Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Zirconium-Mediated C–O Bond Cleavage of Alkenyl Ethers Enables Nickel-Catalyzed C(sp3)–C(sp3) and C(sp3)–C(sp2) Cross-Coupling",
  "title_text": "Zirconium-Mediated C–O Bond Cleavage of Alkenyl Ethers Enables Nickel-Catalyzed C(sp3)–C(sp3) and C(sp3)–C(sp2) Cross-Coupling",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/6k6vb5k3vvejp",
  "venue": "ChemRxiv",
  "versions": []
}