{
  "abstract": "In data analysis of molecular catalysis, molecular shape can be represented by voxel descriptors generated by mapping molecular structures onto a three-dimensional grid according to atomic van der Waals radii. Such voxel representations of molecular shape can be treated as steric molecular fields and are generally used as steric descriptors. However, because electronic perturbations can lead to systematic changes in molecular geometry, steric fields constructed from transition-state (TS) structures may also capture geometric signatures. We therefore examined whether steric fields derived from TS geometries can capture such structural changes associated with electronic perturbations in asymmetric catalysis. Using DFT-calculated TS structures from three asymmetric Michael addition systems, we generated two voxel-based molecular-field representations, steric fields and NPA-charge fields, for the major and minor TS pathways and used them to construct regression models with calculated enantioselectivity (ΔΔ G ‡ ) as the target variable. The resulting steric- and NPA-charge field models showed similar pathway-dependent trends in cross-validated coefficients of determination (q 2 ). The NPA-charge fields revealed distinct charge responses across the three reaction systems, and the associated changes in TS geometry were captured by the steric fields. These results indicate that TS-derived steric fields can encode not only molecular shape but also the geometric changes associated with electronic perturbations, providing simple and interpretable descriptors for data analysis in asymmetric catalysis.",
  "abstract_shown": true,
  "affiliations": [
    "RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, Japan, 351-0198"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 1,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Shigeru Yamaguchi"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/d70epythsd1e5.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009870/v1",
  "fulltext_url": null,
  "id": "d70epythsd1e5",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009870/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|Asymmetric Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7220477470",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009870/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-05",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/d70epythsd1e5.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15009870",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009870/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Asymmetric Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "Transition-State Steric Fields Capture Geometric Signatures Associated with Electronic Perturbations in Asymmetric Catalysis",
  "title_text": "Transition-State Steric Fields Capture Geometric Signatures Associated with Electronic Perturbations in Asymmetric Catalysis",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/d70epythsd1e5",
  "venue": "ChemRxiv",
  "versions": []
}