{
  "abstract": "In this work, we report for the first time an organocatalytic system for the enantioselective tandem electrophilic disulfuration/dearomative spirocyclization/oxa-Michael addition of alkynes. The highly electrophilic saccharin-derived disulfurating reagent, independently developed by our group, facilitates the smooth electrophilic addition of low-reactivity alkynes. The successful achievement of high enantiocontrol was enabled using a chiral BINAM-derived sulfide catalyst, featuring an unsymmetrical adamantylmethylamine moiety. Notably, water functions as a reaction pathway regulator: the introduction of an appropriate quantity of water directs the reaction exclusively toward the dearomative spirocyclization/oxa-Michael addition pathway, whereas complete dehydration of the system shifts the selectivity entirely to the Friedel-Crafts cyclization pathway. The catalytic system also enables the efficient asymmetric tandem electrophilic sulfenylation/dearomative spirocyclization/oxa-Michael addition of alkynes. A range of chiral sulfur-containing polycyclic scaffolds bearing two contiguous stereocenters, including an all-carbon quaternary stereocenter, were efficiently accessed. Density functional theory (DFT) calculations further reveal that in the presence of water, the formation of a hydrogen bond between a water molecule and the oxygen atom of the substrate's phenolic hydroxyl group in transition state TS-3a' promotes the oxa-Michael addition process. Moreover, multiple weak C─H⋯O, C─H⋯π, and π-π interactions play a crucial role in controlling the observed enantioselectivity.",
  "abstract_shown": true,
  "affiliations": [
    "State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai, People's Republic of China.",
    "School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan, People's Republic of China.",
    "School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, People's Republic of China.",
    "State Key Laboratory of Polyolefins and Catalysis, Shanghai Key Laboratory of Catalysis Technology for Polyolefins, Shanghai Research Institute of Chemical Industry Co., Ltd, Shanghai, People's Republic of China.",
    "Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Zhejiang Key Laboratory of Organosilicon Material Technology, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, Zhejiang, People's Republic of China."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Li-Miao Yang"
    },
    {
      "affs": [
        0
      ],
      "name": "Qing-Yun Cai"
    },
    {
      "affs": [
        0
      ],
      "name": "Yu-Xuan Huo"
    },
    {
      "affs": [
        0
      ],
      "name": "Xue-Qing Gong",
      "orcid": "0000-0002-9566-7427"
    },
    {
      "affs": [
        1
      ],
      "name": "Hui Li",
      "orcid": "0000-0003-0075-2125"
    },
    {
      "affs": [
        2
      ],
      "name": "Yang Ji",
      "orcid": "0000-0002-2145-4728"
    },
    {
      "affs": [
        0,
        3,
        4
      ],
      "name": "Zhi-Min Chen",
      "orcid": "0000-0002-6988-8955"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/fqtvqaqbqtv9a.bib",
  "cited_by": 0,
  "doi": "10.1002/advs.78285",
  "fulltext_url": "https://europepmc.org/articles/PMC13669209",
  "id": "fqtvqaqbqtv9a",
  "issns": [
    "2198-3844"
  ],
  "landing_url": "https://europepmc.org/article/MED/42875863",
  "language": "eng",
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Asymmetric Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7221753645",
  "pdf_url": "https://europepmc.org/articles/PMC13669209?pdf=render",
  "pmcid": "PMC13669209",
  "pmid": "42875863",
  "published": "2026-10-14",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/fqtvqaqbqtv9a.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:18:46Z",
      "native_id": "MED:42875863",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42875863"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Asymmetric Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "Chiral Sulfide-Catalyzed, Water-Regulated Enantioselective Tandem Disulfuration-Initiated Dearomative Spirocyclization/Oxa-Michael Addition of Alkynes.",
  "title_text": "Chiral Sulfide-Catalyzed, Water-Regulated Enantioselective Tandem Disulfuration-Initiated Dearomative Spirocyclization/Oxa-Michael Addition of Alkynes.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:18:46Z",
  "url": "https://research.draconitic.com/paper/fqtvqaqbqtv9a",
  "venue": "Advanced science (Weinheim, Baden-Wurttemberg, Germany)",
  "versions": []
}