Conjugative radical-radical coupling: transition-metal-free dialkylation of alkenes

Open AccessCCS ChemistryRESEARCH ARTICLES29 Aug 2025Conjugative radical-radical coupling: transition-metal-free dialkylation of alkenes Chuan Zhu, Jinyan Wan, Jiacheng Chen, Shiguan Wang, Yu Yang, Kai Chen, Patrick J. Walsh, Kai Guo and Chao Feng Chuan Zhu , Jinyan Wan , Jiacheng Chen , Shiguan Wang , Yu Yang , Kai Chen , Patrick J. Walsh , Kai Guo and Chao Feng https://doi.org/10.31635/ccschem.025.202506282 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail An unmet challenge in radical relay difunctionalization of alkenes is incorporation of two discrete transient radicals in a regiocontrolled manner under transition metal-free conditions. Current protocols typically rely on persistent radicals or organometallic surrogates to trap radical adducts, thereby suppressing the undesired reactions but limiting the diversity. The direct use of two transient radicals remains synthetically elusive. We present a visible-light photoredox catalyzed alkene dialkylation strategy via a kinetically guided conjugative radical-radical coupling. This transition-metal-free approach enables two direct C(sp3)−C(sp3) bond formations across the C=C double bond using alkyl and allyl or benzyl radicals. Mechanistic investigations reveal the radical nature of the process. The success of this approach hinges on kinetically controlled radical addition to alkene substrates and the steric protection of the resulting radical adducts. This mild and functional-group tolerant reaction exhibits broad substrate scope and tolerates structurally complex substrates, highlighting its potential for late-stage functionalization. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2025 Chinese Chemical Society Downloaded 220 times PDF downloadLoading ...