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Herein, we report a Pd\u2010catalyzed asymmetric Suzuki\u2013Miyaura coupling for the efficient construction of inherently chiral dibenzo[\n                    <jats:italic>a<\/jats:italic>\n                    ,\n                    <jats:italic>e<\/jats:italic>\n                    ]cyclooctatetraene (dbCOT) diene ligands. This strategy enables rapid access to a diverse range of cyclic diene scaffolds with excellent enantioselectivities (up to 98% ee). Mechanistic investigations reveal that the stereochemical outcome is governed by a sequential dynamic kinetic asymmetric transformation (DyKAT) and enantioenrichment process involving two consecutive coupling events. The resulting inherently chiral dbCOT ligands readily coordinate with transition metals and exhibit excellent catalytic performance in Rh\u2010catalyzed asymmetric additions and Pd\u2010catalyzed atroposelective transformations. This work establishes a catalytic platform for the synthesis of inherently chiral cyclic diene ligands and expands the toolbox of asymmetric catalysis.\n                  <\/jats:p>","DOI":"10.1002\/anie.3092581","type":"journal-article","created":{"date-parts":[[2026,9,19]],"date-time":"2026-09-19T15:56:29Z","timestamp":1789833389000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Taming the Flexible Eight\u2010Membered Ring: Enantioselective Synthesis of Inherently Chiral Dibenzo[\n                    <i>a<\/i>\n                    ,\n                    <i>e<\/i>\n                    ]cyclooctatetraenes Enabled by Pd\u2010Catalyzed Suzuki\u2013Miyaura Cross\u2010Coupling"],"prefix":"10.1002","volume":"65","author":[{"given":"Yu\u2010Kun","family":"Jiang","sequence":"first","affiliation":[{"name":"College of Pharmaceutical Sciences Guizhou University  Guiyang China"},{"name":"College of Chemistry and Chemical 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