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The intermolecular hydrogen atom transfer (HAT) from acetone to triplet state of azolium salts under violet LED irradiation resulted in thermodynamically less favourable (<jats:italic>Z<\/jats:italic>)\u2010\u03b1,\u03b2\u2010unsaturated ketones with up to 99\u2009:\u20091 selectivity <jats:italic>via<\/jats:italic> C\u2212C bond formation. This compelling protocol access the desired \u03b1\u2010C(sp<jats:sup>3<\/jats:sup>)\u2212H acylation product under metal\u2010, ligand\u2010 and oxidant\u2010free conditions on a wide range of substrates.<\/jats:p>","DOI":"10.1002\/chem.202303626","type":"journal-article","created":{"date-parts":[[2023,11,24]],"date-time":"2023-11-24T01:47:38Z","timestamp":1700790458000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Photo\u2010Catalyzed Acyl Azolium Promoted Selective <i>\u03b1<\/i>\u2010C(sp<sup>3<\/sup>)\u2212H Acylation of Acetone via HAT: Access to Thermodynamically Less Favoured (<i>Z<\/i>)\u2010<i>\u03b1,\u03b2\u2010<\/i>Unsaturated Ketones"],"prefix":"10.1002","volume":"30","author":[{"given":"Chandrasekaran","family":"Sivaraj","sequence":"first","affiliation":[{"name":"Department of Chemistry Vellore Institute of Technology  Vellore 632014, Tamil Nadu 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