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Herein, we report the first asymmetric intramolecular rhodium-catalyzed [(3+2+2)] carbocyclization of ACPs, enabled by asymmetric counteranion-directed catalysis (ACDC), to afford bridged tricyclic products with high diastereo- and enantioselectivity. Conventional ligand-controlled approaches failed to provide satisfactory reactivity or enantioinduction, whereas generating a chiral phosphate counteranion in situ from a silver phosphate (e.g., Ag-(S)-TRIP) via salt metathesis with a rhodium complex markedly enhanced enantioselectivity. Enantiomeric excesses of up to 93% were achieved using a matched combination of chiral phosphate and phosphoramidite ligands. The ACDC strategy also enables kinetic resolution of 1,5-diene-tethered ACPs in a new rhodium-catalyzed [(3+2+2)] carbocyclization, providing access to previously inaccessible tricyclic scaffolds with excellent stereocontrol. These results constitute rare examples of highly stereoselective rhodium-catalyzed higher-order carbocyclizations of ACPs and demonstrate that chiral counteranion-directed catalysis can enable asymmetric transition metal-catalyzed [m+n+o] cyclizations that remain inaccessible to conventional chiral-ligand control.<\/jats:p>","DOI":"10.1021\/jacs.6c07021","type":"journal-article","created":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T15:05:00Z","timestamp":1789743900000},"page":"40768-40779","source":"Crossref","is-referenced-by-count":0,"title":["Chiral Counteranion-Directed\nAsymmetric Intramolecular\nRhodium-Catalyzed [(3+2+2)] Carbocyclization Reactions with Alkylidenecyclopropanes"],"prefix":"10.1021","volume":"148","author":[{"given":"Yu","family":"Zhu","sequence":"first","affiliation":[{"name":"Queen\u2019s University , , 90 Bader Lane , ,","place":["Kingston, Canada, K7L 3N6"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zuqing","family":"Mao","sequence":"additional","affiliation":[{"name":"Queen\u2019s University , , 90 Bader Lane , ,","place":["Kingston, Canada, K7L 3N6"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6609-5282","authenticated-orcid":true,"given":"P. Andrew","family":"Evans","sequence":"additional","affiliation":[{"name":"Queen\u2019s University , , 90 Bader Lane , ,","place":["Kingston, Canada, K7L 3N6"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,18]]},"reference":[{"key":"2026093009522769300_cit1a","doi-asserted-by":"publisher","first-page":"2791","DOI":"10.1039\/b913110h","article-title":"Stereoselective Transition Metal-Catalysed Higher-Order\nCarbocyclisation Reactions","volume":"39","author":"Inglesby","year":"2010","journal-title":"Chem. Soc. Rev."},{"key":"2026093009522769300_cit1b","doi-asserted-by":"publisher","first-page":"1072","DOI":"10.1002\/asia.200900712","article-title":"Transition-Metal-Catalyzed\nCycloadditions for the Synthesis of Eight-Membered Carbocycles","volume":"5","author":"Yu","year":"2010","journal-title":"Chem. 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Catal."},{"key":"2026093009522769300_cit6f","doi-asserted-by":"publisher","DOI":"10.1002\/ceur.202500005","article-title":"Palladium-Catalyzed [3+2] Cycloadditions of Alkylidenecyclopropanes\nto Imines: A Direct Approach to Pyrrolidine Scaffolds","volume":"3","author":"Rodin\u0303o","year":"2025","journal-title":"ChemistryEurope"},{"key":"2026093009522769300_cit7","doi-asserted-by":"publisher","first-page":"3952","DOI":"10.1002\/anie.201310232","article-title":"The Isolation and\nCharacterization of a Rhodacycle Intermediate Implicated in Metal-Catalyzed\nReactions of Alkylidenecyclopropanes","volume":"53","author":"Inglesby","year":"2014","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026093009522769300_cit8a","doi-asserted-by":"publisher","first-page":"1411","DOI":"10.1039\/dt9860001411","article-title":"Trimethylenemethane\nMetal Complexes. Part 1. Synthesis of Ruthenium, Osmium, Rhodium,\nand Iridium Complexes","author":"Jones","year":"1986","journal-title":"J. Chem. 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