{
  "abstract": "Despite the widespread utility of carbenoids in boron homologations, practical challenges in accessing unstabilized gem-halometal carbenoids limit their broader synthetic application.A major bottleneck is the historical reliance on gem-dihalide precursors, which restricts the accessible substrate scope.Bypassing gem-dihalides via direct deprotonation of unactivated alkyl halides offers an ideal but historically elusive alternative due to competing base-mediated elimination and substitution reactions.Here we introduce a straightforward deprotonation/boron homologation protocol for both alkyl and α-acyloxy halides using hindered amide bases (over 50 examples).The method was effective for both primary and secondary alkyl halide substrates, tolerating a wide range of functional groups including base-sensitive moieties.The α-acyloxy boronic esters, generated via an efficient aldehyde addition and homologation sequence, readily undergo diverse downstream substitutions with Grignard and organolithium nucleophiles.Finally, combining DFT-based natural bond orbital analysis with statistical modeling of the resulting descriptors, we establish that the energy of the σ(C-H) natural bond orbital predicts the site of deprotonation across every substrate examined, and we trace this selectivity to the interplay of increased scharacter and reduced steric (Pauli) repulsion at the C-H bond geminal to the halogen.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "name": "Cheng-Chun Chen"
    },
    {
      "name": "Chung-En Su"
    },
    {
      "name": "Jin Qian"
    },
    {
      "name": "Griffin W. Batson"
    },
    {
      "name": "Andrew Zahrt"
    },
    {
      "name": "Andy A. Thomas",
      "orcid": "0000-0001-6336-5566"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/9m4j08zr9q5mt.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15002023/v2",
  "fulltext_url": null,
  "id": "9m4j08zr9q5mt",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15002023/v2",
  "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|Organoboron and organosilicon chemistry"
    ]
  ],
  "openalex": "W7223168291",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15002023/v2",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-21",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/9m4j08zr9q5mt.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15002023",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15002023/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organoboron and organosilicon chemistry",
      "subfield": "organic"
    }
  ],
  "title": "Direct Access to Carbenoids from Alkyl and α-Acyloxy Halide`s for Boron Homologations: Method Development and Mechanistic Insights",
  "title_text": "Direct Access to Carbenoids from Alkyl and α-Acyloxy Halide`s for Boron Homologations: Method Development and Mechanistic Insights",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/9m4j08zr9q5mt",
  "venue": "ChemRxiv",
  "versions": []
}