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For an \u03b1\u2010C\u2212H bond activation of ketone, directing groups are also required to control the reaction selectivity. Reported herein is the first \u03b1\u2010alkylation of cyclic ketones in the absence of an amine catalyst and directing group. <jats:sup>1<\/jats:sup>H\u2005NMR, XPS, EPR studies and DFT calculations indicate that an \u03b1\u2010carbon radical intermediate is formed through direct and selective activation of the inert \u03b1\u2010C\u2212H bond of ketones chelating on the surface of colloidal quantum dots (QDs). Such an interaction is essential for weakening the C\u2212H bond, as exemplified, using CdSe QDs as the sole photocatalyst to execute \u03b1\u2010C\u2212H alkylation of cyclic ketones under visible\u2010light irradiation. Without an amine catalyst and directing group, the high step\u2010 and atom\u2010economy transformation under redox\u2010neutral condition opens a new way for \u03b1\u2010C\u2212H functionalization of ketones in carbonyl chemistry.<\/jats:p>","DOI":"10.1002\/anie.202305679","type":"journal-article","created":{"date-parts":[[2023,5,23]],"date-time":"2023-05-23T08:50:37Z","timestamp":1684831837000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Amine\u2010Free, Directing\u2010Group\u2010Free and Redox\u2010Neutral \u03b1\u2010Alkylation of Saturated Cyclic Ketones"],"prefix":"10.1002","volume":"62","author":[{"given":"Jia","family":"Qiao","sequence":"first","affiliation":[{"name":"Key Laboratory of Photochemical Conversion and Optoelectronic Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences  Beijing 100190 China"},{"name":"School of Future 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