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Herein, we report the discovery of an unprecedented group of minor plant sesterterpenoids, gracilisoids B\u2212E (\n                    <jats:bold>2\u20135<\/jats:bold>\n                    ), which feature two types of highly functionalized bicyclo[3.2.0]heptane carbon skeletons, along with their biogenetically related precursor gracilisoid A (\n                    <jats:bold>1<\/jats:bold>\n                    ), from a Lamiaceae ethnomedicinal plant,\n                    <jats:italic>Eurysolen gracilis<\/jats:italic>\n                    . To confirm their structures and obtain adequate materials for biological research, the asymmetric total syntheses of gracilisoids A\u2212E (\n                    <jats:bold>1\u20135<\/jats:bold>\n                    ) and four new biogenetically\u2010related congeners gracilisoids F\u2212I (\n                    <jats:bold>6\u20139<\/jats:bold>\n                    ) were achieved from commercially available (\u2212)\u2010citronellal by a bioinspired approach that involves a Norrish\u2010Yang photocyclization\/\u03b1\u2010hydroxy ketone rearrangement tandem reaction and a late\u2010stage biomimetic photooxidation as key steps. Biological investigations revealed that gracilisoids A\u2212I (\n                    <jats:bold>1\u20139<\/jats:bold>\n                    ) significantly inhibited IFN\u2010\u03b3 production and\/or T cell proliferation probably through inhibition of the STAT pathway. The findings herald the potential of these gracilisoids as novel immunosuppressive agents, and efficient synthetic approaches will facilitate a comprehensive evaluation of their value in future drug development.\n                  <\/jats:p>","DOI":"10.1002\/anie.202421497","type":"journal-article","created":{"date-parts":[[2025,1,13]],"date-time":"2025-01-13T06:07:27Z","timestamp":1736748447000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Discovery and Total Synthesis of a New Class of Minor Immunosuppressive Plant Sesterterpenoids"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4375-5457","authenticated-orcid":false,"given":"Yu","family":"Zheng","sequence":"first","affiliation":[{"name":"State Key Laboratory of Phytochemistry and Natural Medicines, and Yunnan Key Laboratory of Natural Medicinal Chemistry Kunming Institute of Botany, Chinese Academy of Sciences  Kunming 650201 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin\u2010Lin","family":"Teng","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Phytochemistry and Natural Medicines, and Yunnan Key Laboratory of Natural Medicinal Chemistry Kunming Institute of Botany, Chinese Academy of Sciences  Kunming 650201 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ting\u2010Ting","family":"Zhou","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Phytochemistry and Natural Medicines, and Yunnan Key Laboratory of Natural Medicinal Chemistry Kunming Institute of Botany, Chinese Academy of Sciences  Kunming 650201 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhi\u2010Wei","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Phytochemistry and Natural Medicines, and Yunnan Key Laboratory of Natural Medicinal Chemistry Kunming Institute of Botany, Chinese Academy of Sciences  Kunming 650201 P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing 100049 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kai","family":"Guo","sequence":"additional","affiliation":[{"name":"Innovative Institute of Chinese Medicine and Pharmacy Chengdu University of Traditional Chinese Medicine  Chengdu 611137 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Li","sequence":"additional","affiliation":[{"name":"Innovative Institute of Chinese Medicine and Pharmacy Chengdu University of Traditional Chinese Medicine  Chengdu 611137 P. R. 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