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Various approaches have been developed to address challenges in amide transformations. Nonetheless, most methods use activated amides, organometallic reagents or transition metal catalysts. Here, we report the direct alkylation of <jats:italic>N,N<\/jats:italic>-dialkyl benzamides with methyl sulfides promoted by the readily available base LDA (lithium diisopropylamide). This approach successfully achieves an efficient and selective synthesis of \u03b1-sulfenylated ketones without using transition-metal catalysts or organometallic reagents. Preliminary mechanism studies reveal that the deprotonative aroylation of methyl sulfides is promoted by the directed <jats:italic>ortho<\/jats:italic>-lithiation of the\u00a0tertiary benzamide with LDA.<\/jats:p>","DOI":"10.1038\/s42004-021-00575-2","type":"journal-article","created":{"date-parts":[[2021,9,27]],"date-time":"2021-09-27T10:20:00Z","timestamp":1632738000000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Direct alkylation of N,N-dialkyl benzamides with methyl sulfides under transition metal-free conditions"],"prefix":"10.1038","volume":"4","author":[{"given":"Can-Can","family":"Bao","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hui-Zhen","family":"Du","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan-Long","family":"Luo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0686-4945","authenticated-orcid":false,"given":"Bing-Tao","family":"Guan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2021,9,27]]},"reference":[{"key":"575_CR1","unstructured":"Greenberg, A., Breneman, C. 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