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Adv."],"published-print":{"date-parts":[[2026,7,10]]},"abstract":"<jats:p>\n                    In the past two decades, oxidant-free, ligand-enabled gold(I)\/gold(III) [Au(I)\/Au(III)] catalysis has become a potential complement to palladium(0)\/palladium(II) [Pd(0)\/Pd(II)] catalysis in diverse transformation, yet broadly general ligands for Au(I)\/Au(III) catalysis remain lacking. Herein, we report a platform for ligand-enabled Au(I)\/Au(III) catalysis through the rational development of hemilabile ImQun N-heterocyclic carbene (NHC) nitrogen (N),carbon (C) ligands (ImQun\u00a0=\u00a0imidazo[1,5-\n                    <jats:italic toggle=\"yes\">a<\/jats:italic>\n                    ]quinoline). Intriguingly, the best Au catalyst ImQunDippNMe\n                    <jats:sub>2<\/jats:sub>\n                    AuCl features the shortest distances between the chelating N atom and the Au center for oxidant-free reaction paradigms. The excellent activity has been demonstrated in alkene difunctionalization via the oxidant-free Au(I)\/Au(III) cycle through C\u2500O, C\u2500N, and C\u2500C bond formation, including highly challenging aromatic olefins (&gt;60 examples) and late-stage modification of complex pharmaceuticals (&gt;15 examples). Comprehensive density functional theory (DFT) studies have provided fundamental insight into the reaction mechanism and highlight the central effect of this NHC on the Au(I)\/Au(III) redox cycle. The facile access to hemilabile, closely coordinating NHC will enable accelerated development of Au(I)\/Au(III) oxidant-free reactivity paradigms using powerful Au catalysis.\n                  <\/jats:p>","DOI":"10.1126\/sciadv.aed3424","type":"journal-article","created":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T17:58:37Z","timestamp":1783706317000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":1,"title":["Oxidant-free Au(I)\/Au(III) catalysis: Rational development of hemilabile proximity-guided N-heterocyclic carbenes"],"prefix":"10.1126","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4266-0616","authenticated-orcid":true,"given":"Pengcheng","family":"Gao","sequence":"first","affiliation":[{"name":"Departments of Pharmacological Sciences, Icahn School of Medicine at Mount Sinai, New York, NY 10029, USA."},{"name":"Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jihong","family":"Xu","sequence":"additional","affiliation":[{"name":"Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenchao","family":"Chu","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2567-420X","authenticated-orcid":true,"given":"Yanhong","family":"Liu","sequence":"additional","affiliation":[{"name":"Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8443-3561","authenticated-orcid":true,"given":"Alejandro","family":"Cervantes-Reyes","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7070-2468","authenticated-orcid":true,"given":"Elwira","family":"Bisz","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Opole University, 48 Oleska Street, Opole 45-052, Poland."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"B\u0142a\u017cej","family":"Dziuk","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Science and Technology, Norwida 4\/6, Wroclaw 50-373, Poland."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Roger","family":"Lalancette","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5436-7284","authenticated-orcid":true,"given":"Roman","family":"Szostak","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Wroclaw University, F. 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