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Here, we report an asymmetric benzylic C\u2212H acylation of alkylarenes employing carboxylic acids as acyl surrogates for the synthesis of \u03b1-aryl ketones via nickel and photoredox dual catalysis. This mild yet straightforward protocol transforms a diverse array of feedstock carboxylic acids and simple alkyl benzenes into highly valuable \u03b1-aryl ketones with high enantioselectivities. The utility of this method is showcased in the gram-scale synthesis and late-stage modification of medicinally relevant molecules. Mechanistic studies suggest a photocatalytically generated bromine radical can perform benzylic C\u2212H cleavage to activate alkylarenes as nucleophilic coupling partners which can then engage in a nickel-catalyzed asymmetric acyl cross-coupling reaction. This bromine-radical-mediated C\u2212H activation strategy can be also applied to the enantioselective coupling of alkylarenes with chloroformate for the synthesis of chiral \u03b1-aryl esters.<\/jats:p>","DOI":"10.1038\/s41467-021-23887-2","type":"journal-article","created":{"date-parts":[[2021,6,10]],"date-time":"2021-06-10T10:04:33Z","timestamp":1623319473000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":127,"title":["Asymmetric benzylic C(sp3)\u2212H acylation via dual nickel and photoredox catalysis"],"prefix":"10.1038","volume":"12","author":[{"given":"Leitao","family":"Huan","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5333-5339","authenticated-orcid":false,"given":"Xiaomin","family":"Shu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weisai","family":"Zu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"De","family":"Zhong","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1785-4128","authenticated-orcid":false,"given":"Haohua","family":"Huo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2021,6,10]]},"reference":[{"key":"23887_CR1","doi-asserted-by":"publisher","first-page":"72","DOI":"10.1021\/op960009e","volume":"1","author":"PJ Harrington","year":"1997","unstructured":"Harrington, P. 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