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Herein, we present a strong Lewis acidic diethylsilylium catalysis that enables efficient reductive sulfonamidation of functionalized ketones, including \u03b2\u2010ketoesters, to access alkyl \u03b2\u2010amino esters. The active diethylsilylium ion pair ([Et\n                    <jats:sub>2<\/jats:sub>\n                    HSi]\n                    <jats:sup>+<\/jats:sup>\n                    [B(C\n                    <jats:sub>6<\/jats:sub>\n                    F\n                    <jats:sub>5<\/jats:sub>\n                    )\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sup>\u2013<\/jats:sup>\n                    ), in situ generated via hydride abstraction from diethylsilane by trityl tetrakis(pentafluorophenyl)borate, displays a remarkably enhanced catalytic performance. Diethylsilane functions dually as the reductant and precursor of the silylium species. Operating under solvent\u2010, metal\u2010, hydrogen\u2010, and additive\u2010free conditions, the protocol offers broad substrate scope and excellent scalability, exemplified by a concise three\u2010step, multi\u2010gram synthesis of the antidiabetic drug sitagliptin (&gt; 4\u00a0g). Combined computational, NMR, and HR\u2010MS analyses reveal that the remarkable Lewis acidity of the secondary silylium ion enables activation of challenging substrates and affords exceptional selectivity. A mechanistic understanding of this process provides the foundation for a practical and sustainable catalytic system that expands the frontier of silylium\u2010mediated C\u2500N bond formation.\n                  <\/jats:p>","DOI":"10.1002\/advs.75783","type":"journal-article","created":{"date-parts":[[2026,5,26]],"date-time":"2026-05-26T14:34:49Z","timestamp":1779806089000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["A Strong Lewis Acidic Diethylsilylium Catalyst for Direct Sulfonamidation of Challenging Ketones"],"prefix":"10.1002","volume":"13","author":[{"given":"Woo Hee","family":"Kim","sequence":"first","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Muhammad","family":"Israr","sequence":"additional","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon Republic of 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