{
  "abstract": "Grignard additions to a TADDOL-derived -ketiminophosphonate display pronounced reagent-dependent diastereoselectivity, with dr values of 94:6 for methylmagnesium bromide and 55:45 for 2-naphthylmagnesium bromide. In this study, we carried out DFT calculations showing that dimeric Grignard models coordinate to the phosphoryl and sulfonyl regions of the substrate, restricting C–P bond rotation and enabling facial differentiation. The nature of the Grignard reagent modulates the organisation of the reactive complex and the relative stability of the competing transition structures, providing a mechanistic rationale for the contrasting stereochemical",
  "abstract_shown": true,
  "affiliations": [
    "Department of Organic Chemistry I, Faculty of Pharmacy, University of the Basque Country, UPV/EHU, Paseo de la Universidad 7, Vitoria-Gasteiz, Spain, 01006",
    "Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, United Kingdom, OX1 3TA",
    "Ikerbasque, Basque Foundation for Science, Plaza Euskadi 5, Bilbao, Spain, 48009",
    "Department of Organic Chemistry I, Donostia International Physics Centre (DIPC, UPV/EHU, Paseo Manuel de Lardizabal, 3, Donostia-San Sebastián, Spain, 20018"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Adrián López-Francés",
      "orcid": "0000-0002-6363-2246"
    },
    {
      "affs": [
        0
      ],
      "name": "Javier Vicario",
      "orcid": "0000-0002-8976-0991"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Abel de Cózar",
      "orcid": "0000-0001-8430-4076"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/202q2b68d825j.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009360/v1",
  "fulltext_url": null,
  "id": "202q2b68d825j",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009360/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|Organophosphorus compounds synthesis"
    ]
  ],
  "openalex": "W7214065712",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009360/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/202q2b68d825j.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009360",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009360/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organophosphorus compounds synthesis",
      "subfield": "organic"
    }
  ],
  "title": "Origin of Reagent-Dependent Diastereoselectivity in Grignard Additions to a TADDOL-Derived α-Ketiminophosphonate",
  "title_text": "Origin of Reagent-Dependent Diastereoselectivity in Grignard Additions to a TADDOL-Derived α-Ketiminophosphonate",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/202q2b68d825j",
  "venue": "ChemRxiv",
  "versions": []
}