Wang, DingyiDingyiWangYuan, BinbinBinbinYuanXu, JiaweiJiaweiXuAckermann, LutzLutzAckermann2023-03-042023-03-042023-04-13https://resolver.sub.uni-goettingen.de/purl?gro-2/122041An electrochemical strategy for the dual functionalizations of unactivated alkenes through an intramolecular migration process was realized in the absence of sacrificial chemical oxidants and noble-metal catalysts under mild reaction conditions. The electrochemistry enabled a (hetero)aryl migration while providing access to alkenyl/alkynyl-migration products. Thus, electricity was employed for the formation of functionalized fluoroalkyl radicals through activation of C−H/C−Br bonds from fluorinated esters. Thereby, we obtained a variety of di and mono-fluorinated alkyl products with good functional group tolerance as well as chemo, and regioselectivities. Likewise, defluorinative allylation of α-carbonyl alkyl bromides proved viable. The reaction mechanism was established by experiments and computations.enCC BY-NC 4.0http://onlinelibrary.wiley.com/termsAndConditions#vorjournal_article10.1002/chem.2023006002023-07-12