{
  "abstract": "Nitrogen-containing molecules are ubiquitous in pharmaceuticals, natural products, ligands, and functional materials, sustaining continued interest in efficient C-N bond-forming strategies. Although electrophilic amination has emerged as a powerful complement to classical nucleophilic substitution and cross-coupling methods, the transfer of structurally complex NH-alkyl groups remains limited by the lack of general access to suitably reactive electrophilic aminating reagents. Herein, we report the direct single-step oxidation of primary amines to N-alkyl-O-mesyl hydroxylamines using dimesyl peroxide (MPO). This transformation achieves an umpolung of otherwise nucleophilic amines and provides rapid access to synthetically versatile electrophilic nitrogen building blocks under mild conditions. A broad substrate scope enables the preparation of structurally complex and chiral N-alkyl-O-mesyl hydroxylamines, including derivatives of amino acids, natural products, and pharmaceuticals. These reagents were directly deployed in established electrophilic amination manifolds, including arene C-H amination, olefin aziridination, and aza-Rubottom oxidation, enabling the transfer of structurally complex and chiral amine fragments. Collectively, this work establishes a general strategy for converting readily available primary amines into electrophilic nitrogen fragments for efficient C-N bond formation and N-electrophilic fragment coupling.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, BioScience Research Collaborative, Rice University, 6500 Main Street, Rm 380, Houston, Texas77030, United States.",
    "Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah84602, United States."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Mats Georg",
      "orcid": "0009-0006-4631-2853"
    },
    {
      "affs": [
        0
      ],
      "name": "Young-Do Kwon",
      "orcid": "0000-0002-7515-6021"
    },
    {
      "affs": [
        0
      ],
      "name": "Mathias Boeckle"
    },
    {
      "affs": [
        1
      ],
      "name": "Dongdong Yang"
    },
    {
      "affs": [
        1
      ],
      "name": "Daniel H Ess",
      "orcid": "0000-0001-5689-9762"
    },
    {
      "affs": [
        0
      ],
      "name": "László Kürti"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/3cmwkzbdrvfs0.bib",
  "cited_by": 0,
  "doi": "10.1021/jacs.6c14811",
  "fulltext_url": "https://europepmc.org/articles/PMC13674238",
  "id": "3cmwkzbdrvfs0",
  "issns": [
    "0002-7863",
    "1520-5126"
  ],
  "landing_url": "https://europepmc.org/article/MED/42913601",
  "language": "eng",
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Synthesis and Catalytic Reactions"
    ]
  ],
  "openalex": "W7219695198",
  "pdf_url": "https://europepmc.org/articles/PMC13674238?pdf=render",
  "pmcid": "PMC13674238",
  "pmid": "42913601",
  "published": "2026-10-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/3cmwkzbdrvfs0.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:20:14Z",
      "native_id": "MED:42913601",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42913601"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Synthesis and Catalytic Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Complex Fragment Coupling via O-Mesyl Hydroxylamines: Direct Conversion of Primary Amines to Electrophilic Aminating Agents.",
  "title_text": "Complex Fragment Coupling via O-Mesyl Hydroxylamines: Direct Conversion of Primary Amines to Electrophilic Aminating Agents.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:20:14Z",
  "url": "https://research.draconitic.com/paper/3cmwkzbdrvfs0",
  "venue": "Journal of the American Chemical Society",
  "versions": []
}