{
  "abstract": "We disclose a highly regio- and enantioselective Ir(I)-catalyzed hydroamination of 1,1-disubstituted allenes, providing a broadly applicable access to α-tertiary chiral allylic amines, very relevant structural motifs that are mostly inaccessible through other enantioselective strategies. The method employs an a-aminopyridine as nucleophile, and displays a broad substrate scope, accommodating both aryl- and alkyl-substituted allenes. Removal of the pyridine moiety of the products yields synthetically challenging primary allylic amines bearing α-tetrasubstituted stereocenters. Notably, addition of i -PrOH after completion of the hydroamination enables an in situ transfer hydrogenation of the generated alkene to deliver the corresponding a-tertiary saturated amines with equally high selectivities. The use of trisubstituted allenes in the hydroamination protocol is also feasible, affording in this case a-secondary allylic amines, also with high selectivities. Finally, experimental and computational mechanistic studies support a hydrometalation/C–N bond-forming sequence as the preferred reaction pathway, with the C-N reductive elimination step identified as enantio- and TOF-determining.",
  "abstract_shown": true,
  "affiliations": [
    "Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departa-mento de Química Orgánica.",
    "Universidade de Santiago de Compostela",
    "Misión Biológica de Galicia (MBG), Consejo Superior de Investigaciones Científicas (CSIC)"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 4,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Alejandro Rey"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "María Puente"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "José L Mascareñas"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Fernando López",
      "orcid": "0000-0002-0235-6858"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/c5y08bt8m2y8e.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.10001679/v4",
  "fulltext_url": null,
  "id": "c5y08bt8m2y8e",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.10001679/v4",
  "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|Catalytic Alkyne Reactions"
    ]
  ],
  "openalex": "W7222743078",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.10001679/v4",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-16",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/c5y08bt8m2y8e.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.10001679",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.10001679/v4"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic Alkyne Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Iridium-Catalyzed Regio- and Enantioselective Hydroamination of Allenes: Direct Access to α-Tertiary Chiral Allylic Amines",
  "title_text": "Iridium-Catalyzed Regio- and Enantioselective Hydroamination of Allenes: Direct Access to α-Tertiary Chiral Allylic Amines",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/c5y08bt8m2y8e",
  "venue": "ChemRxiv",
  "versions": []
}