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Our approach highlights (1) a TEMPO+BF4\u2013-mediated oxidative Nazarov cyclization that rapidly assembles the hydrindane core bearing the key C15-quaternary center; (2) a Stoltz decarboxylative allylic alkylation to highly diastereoselectively install the adjacent C3-quaternary center; (3) a strategic intramolecular carbon atom transfer that overcomes formidable challenges of both homologation and stereochemical control encountered with conventional approaches; and (4) an ene-yne-ene cascade metathesis that efficiently forges the [5\u20137] bicyclic system and ultimately the entire tetracyclic skeleton, representing the first example of constructing a highly strained trans-fused [5\u20135] bicyclic ring system via a metathesis reaction.<\/jats:p>","DOI":"10.1021\/jacs.6c09948","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T20:01:34Z","timestamp":1786046494000},"page":"34696-34702","source":"Crossref","is-referenced-by-count":0,"title":["Asymmetric Total Synthesis\nof Venezuelaene A via TEMPO+BF4\u2013-Mediated Oxidative\nNazarov Cyclization and Cascade Metathesis"],"prefix":"10.1021","volume":"148","author":[{"given":"Sujun","family":"Xie","sequence":"first","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Axiao","family":"Tao","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qian","family":"Wang","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jia-Dong","family":"Yu","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chengqing","family":"Ning","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5304-7350","authenticated-orcid":true,"given":"Jing","family":"Xu","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,6]]},"reference":[{"key":"2026081910211396500_cit1a","doi-asserted-by":"publisher","first-page":"5846","DOI":"10.1021\/acscatal.0c01575","article-title":"Fragrant Venezuelaenes\nA and B with a 5\u20135\u20136\u20137 Tetracyclic Skeleton:\nDiscovery, Biosynthesis, and Mechanisms of Central Catalysts","volume":"10","author":"Li","year":"2020","journal-title":"ACS Catal."},{"key":"2026081910211396500_cit1b","doi-asserted-by":"publisher","first-page":"4001","DOI":"10.1038\/s41467-023-39706-9","article-title":"Molecular insights into the catalytic\npromiscuity of a bacterial diterpene synthase","volume":"14","author":"Li","year":"2023","journal-title":"Nat. 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