{
  "abstract": "The cleavage of ether C–O bonds by transition-metal complexes has attracted considerable attention, but catalytic cleavage of vinyl ether C(sp²)–O bonds is largely unexplored. Herein we report the dehydrovinylation of alkyl vinyl ethers catalyzed by a pincer-ligated osmium complex. Primary alkyl vinyl ethers undergo C–O bond cleavage to afford ethylene and the corresponding aldehydes, which undergo tandem Tishchenko coupling to yield esters. Secondary alkyl vinyl ethers undergo dehydrovinylation to afford ethylene and ketones. Experimental observations and density functional theory calculations support a mechanism involving insertion of the vinyl ether C=C bond into an Os–H bond, followed by β-alkoxy elimination and β-hydride elimination to form the carbonyl product. These results establish a new mode of catalytic C(sp²)–O bond cleavage and demonstrate its application in a tandem dehydrovinylation–Tishchenko transformation.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry and Chemical Biology",
    "Rutgers The State University of New Jersey, New Brunswick",
    "Department of Chemistry",
    "Rutgers University–Camden"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 4,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Ashish Parihar",
      "orcid": "0000-0003-1049-0077"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Soham Chakraborty",
      "orcid": "0000-0002-0846-4390"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Santanu Malakar",
      "orcid": "0000-0002-3838-5095"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Alan S. Goldman",
      "orcid": "0000-0002-2774-710X"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/3f594xfzc58za.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010232/v1",
  "fulltext_url": null,
  "id": "3f594xfzc58za",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010232/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|Organometallic Complex Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7221511216",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010232/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-11",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/3f594xfzc58za.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010232",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010232/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organometallic Complex Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "Catalytic C–O Bond Cleavage of Vinyl Ethers via Dehydrovinylation and Tandem Tishchenko Coupling",
  "title_text": "Catalytic C–O Bond Cleavage of Vinyl Ethers via Dehydrovinylation and Tandem Tishchenko Coupling",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/3f594xfzc58za",
  "venue": "ChemRxiv",
  "versions": []
}