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However, accessing all three congeners under a single chemodivergent protocol remains challenging due to the inherent reactivity difference between C\uf8feC and C\uf8feO bonds. In general, the lower\u2010energy 1,4\u2010addition of a metal hydride preferentially reduces the C\uf8feC bond over the C\uf8feO bond. Thus, allylic alcohols remain inaccessible with current methodologies. The reactivity of a catalytic reaction can be enhanced under an aqueous medium that involves water as a reactant. Additionally, the unique inherent H\u2010bonding network in H<jats:sub>2<\/jats:sub>O medium can unlock new reactivity patterns with added sustainability. Herein, a proton\u2010responsive Ir(III) complex catalyzed, base\u2010free, chemodivergent CTH of enones utilizing methyl formate (MF) under aqueous media is demonstrated, enabling precise control over 1,4\u2010 versus 1,2\u2010insertion into the Ir\uf8ffH species. This strategy enables the selective synthesis of all possible CTH products with high efficiency. Furthermore, a series of experimental studies provides deeper insights into the diversity of product formation, which are further supported by DFT calculations.<\/jats:p>","DOI":"10.1002\/cssc.202500844","type":"journal-article","created":{"date-parts":[[2025,7,8]],"date-time":"2025-07-08T10:34:09Z","timestamp":1751970849000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Ir(III) Complex\u2010Catalyzed Base\u2010Free Chemodivergent Transfer Hydrogenation of Enones Utilizing Methyl Formate under Aqueous Media: Modulating 1,4\u2010 versus 1,2\u2010Insertion"],"prefix":"10.1002","volume":"18","author":[{"given":"Anirban","family":"Sau","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Divya","family":"Mahapatra","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tanmoy Kumar","family":"Ghosh","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arunima","family":"Maity","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dibyajyoti","family":"Panja","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sadhan","family":"Dey","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4227-294X","authenticated-orcid":false,"given":"Sabuj","family":"Kundu","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Kanpur  Kanpur Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,8,7]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00125B"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00203"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CS00101B"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jnatprod.8b01022"},{"key":"e_1_2_7_4_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr200016m"},{"key":"e_1_2_7_5_1","first-page":"65","author":"Carey F. 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