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Here, we demonstrate a tandem electrochemical\/electrophotocatalytic reaction to olefinate aldehydes and ketones with a broad range of unactivated alkenes. This method involves the oxidation-induced denitrogenation of cyclic diazenes to form 1,3-distonic radical cations that rearrange to yield the olefin products. This olefination reaction is enabled by an electrophotocatalyst that inhibits back-electron transfer to the radical cation intermediate, thus allowing for the selective formation of olefin products. The method is compatible with a wide range of aldehydes, ketones, and alkene partners.<\/jats:p>","DOI":"10.1126\/sciadv.adg3026","type":"journal-article","created":{"date-parts":[[2023,4,14]],"date-time":"2023-04-14T17:58:17Z","timestamp":1681495097000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":25,"title":["Olefination of carbonyls with alkenes enabled by electrophotocatalytic generation of distonic radical cations"],"prefix":"10.1126","volume":"9","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4172-0579","authenticated-orcid":true,"given":"Keri A.","family":"Steiniger","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7720-3290","authenticated-orcid":true,"given":"Tristan H.","family":"Lambert","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","unstructured":"T. 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