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Although the alkynyl group is a versatile synthetic handle for diverse functionalizations, the catalytic asymmetric synthesis of alkynyl-substituted all-carbon quaternary centers is significantly underdeveloped. Herein, we report an unprecedented asymmetric propargylic substitution of tertiary propargylic carbonates with \u03b1-hydroxy ketones, enabled by a synergistic B\/Pd dual-catalytic system. Unlike traditional Pd-catalyzed pathways that typically favor allene formation, this protocol uniquely preserves the alkyne moiety to deliver alkynyl-substituted all-carbon quaternary stereocenters bearing a vicinal tertiary stereocenter with excellent diastereo- and enantiocontrol. Notably, the catalytic system effectively overcomes the inherent steric congestion of coupling two bulky partners and achieves the precise discrimination between two sterically and electronically similar alkyl groups (e.g., methyl vs ethyl) on the propargylic carbon. Chiral phosphoramidite-palladium catalysts play a critical role in creating a differentiated chiral environment to achieve exceptional levels of enantioselectivity.<\/jats:p>","DOI":"10.1021\/jacs.6c07657","type":"journal-article","created":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T17:02:01Z","timestamp":1786986121000},"page":"35717-35728","source":"Crossref","is-referenced-by-count":1,"title":["B\/Pd-Catalyzed Asymmetric\nPropargylic Substitution\nfor Vicinal Quaternary\/Tertiary Stereocenters"],"prefix":"10.1021","volume":"148","author":[{"given":"Zhihe","family":"Cen","sequence":"first","affiliation":[{"name":"Shanghai University , , ,","place":["Shanghai, China, 200444"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hua","family":"Liang","sequence":"additional","affiliation":[{"name":"Shanghai University , , ,","place":["Shanghai, China, 200444"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guanzhen","family":"Zhao","sequence":"additional","affiliation":[{"name":"Shanghai University , , ,","place":["Shanghai, China, 200444"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fan","family":"Wu","sequence":"additional","affiliation":[{"name":"Shanghai University , , ,","place":["Shanghai, China, 200444"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5230-782X","authenticated-orcid":true,"given":"Xinyao","family":"Li","sequence":"additional","affiliation":[{"name":"Shanghai University , , ,","place":["Shanghai, China, 200444"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7179-4280","authenticated-orcid":true,"given":"Xiaoyu","family":"Wu","sequence":"additional","affiliation":[{"name":"Shanghai University , , ,","place":["Shanghai, China, 200444"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,17]]},"reference":[{"key":"2026090104514792900_cit1a","doi-asserted-by":"publisher","first-page":"181","DOI":"10.1038\/nature14007","article-title":"Catalytic enantioselective synthesis\nof quaternary carbon stereocenters","volume":"516","author":"Quasdorf","year":"2014","journal-title":"Nature"},{"key":"2026090104514792900_cit1b","doi-asserted-by":"publisher","first-page":"740","DOI":"10.1021\/ar5004658","article-title":"Catalytic\nenantioselective construction of quaternary stereocenters: assembly\nof key building blocks for the synthesis of biologically active molecules","volume":"48","author":"Liu","year":"2015","journal-title":"Acc. Chem. Res"},{"key":"2026090104514792900_cit1c","doi-asserted-by":"publisher","first-page":"7330","DOI":"10.1021\/acs.chemrev.6b00094","article-title":"Catalytic\nenantioselective desymmetrization reactions to all-carbon quaternary\nstereocenters","volume":"116","author":"Zeng","year":"2016","journal-title":"Chem. Rev"},{"key":"2026090104514792900_cit4d","unstructured":"(d)\n          \n            \n              Rudolf, G. C.; Seet, M.; Mueller, B.; Grammenos, W.; Merget, B. J.; Koch, A.; Riediger, N.; Wiebe, C.; Grote, T.; Lohmann, J. K.; et al.\n          Pyridine derivatives\nand their use as fungicides and their preparation, WO 2,020,244,969\nA12020."},{"key":"2026090104514792900_cit2a","doi-asserted-by":"publisher","first-page":"2682","DOI":"10.1021\/ja410424g","article-title":"All-carbon quaternary\nstereogenic centers in acyclic systems through the creation of several\nC\u2013C bonds per chemical step","volume":"136","author":"Marek","year":"2014","journal-title":"J. Am. Chem.\nSoc"},{"key":"2026090104514792900_cit2b","doi-asserted-by":"publisher","first-page":"4593","DOI":"10.1039\/c0cc05222a","article-title":"Enantioselective synthesis\nof all-carbon quaternary stereogenic centers in acyclic systems","volume":"47","author":"Das","year":"2011","journal-title":"Chem. Commun"},{"key":"2026090104514792900_cit2c","doi-asserted-by":"publisher","first-page":"12564","DOI":"10.1021\/acs.chemrev.7b00385","article-title":"Acyclic quaternary carbon stereocenters\nvia enantioselective transition metal catalysis","volume":"117","author":"Feng","year":"2017","journal-title":"Chem. Rev"},{"key":"2026090104514792900_cit3a","doi-asserted-by":"publisher","first-page":"271","DOI":"10.1021\/cr950010w","article-title":"Carbene\u2013alkyne\u2013alkene\nCyclization Reactions","volume":"96","author":"Harvey","year":"1996","journal-title":"Chem. 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