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During the ketone synthesis, various functional groups, such as carbonyl (ketones, esters, and amides), O\u2010protecting groups, halogens, and heteroarenes, were tolerated to afford multifunctionalized ketones in excellent yields. This copper\u2010mediated ketone synthesis could be applied to the synthesis of not only gluconolactone\u2010derived ketone <jats:bold>6<\/jats:bold>, a synthetic intermediate in the transformation to the SGLT2 inhibitor canagliflozin, but also thiolactol <jats:bold>8<\/jats:bold>, a valuable synthetic intermediate for (+)\u2010biotin. Control experiments on an isolated diphenylcuprate(I), [CuPh<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (<jats:bold>12<\/jats:bold>), and DFT calculations revealed that this ketone synthesis proceeded by oxidative addition of the C\u2212S bond of thioesters to [CuPh<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup>, while reductive elimination from the Cu<jats:sup>III<\/jats:sup> intermediate produced the corresponding ketone and an inactive species [(RS)CuPh]<jats:sup>\u2212<\/jats:sup>, the latter reacted with [CuPh]<jats:sub>4<\/jats:sub> (<jats:bold>11<\/jats:bold>) to regenerate the reactive diphenylcuprate(I).<\/jats:p>","DOI":"10.1002\/chem.202200474","type":"journal-article","created":{"date-parts":[[2022,3,16]],"date-time":"2022-03-16T00:35:58Z","timestamp":1647390958000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Diarylcuprates for Selective Syntheses of Multifunctionalized Ketones from Thioesters under Mild Conditions"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4586-6572","authenticated-orcid":false,"given":"Daiki","family":"Kato","sequence":"first","affiliation":[{"name":"Department of Chemistry Graduate School of Engineering Science Osaka University  560-8531 Toyonaka Osaka Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tomoya","family":"Murase","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Engineering Science Osaka University  560-8531 Toyonaka Osaka Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jalindar","family":"Talode","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Engineering Science Osaka University  560-8531 Toyonaka Osaka Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5589-7375","authenticated-orcid":false,"given":"Haruki","family":"Nagae","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Engineering Science Osaka University  560-8531 Toyonaka Osaka Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2942-7705","authenticated-orcid":false,"given":"Hayato","family":"Tsurugi","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Engineering Science Osaka University  560-8531 Toyonaka Osaka Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Masahiko","family":"Seki","sequence":"additional","affiliation":[{"name":"Marketing Group Research &amp; 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