Institut für Organische und Biomolekulare Chemie and Wöhler Research Institute for Sustainable Chemistry, Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.
DZHK (German Centrefor Cardiovascular Research), Potsdamer Straße 58, 10785, Berlin, Germany.
Chemistry. 2023 May 26;29(30):e202300600. doi: 10.1002/chem.202300600. Epub 2023 Apr 13.
An 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.
一种通过分子内迁移过程对未活化烯烃进行双重官能化的电化学策略在温和的反应条件下，无需牺牲化学氧化剂和贵金属催化剂即可实现。电化学能够进行（杂）芳基迁移，同时获得烯基/炔基迁移产物。因此，通过氟化酯中 C-H/C-Br 键的活化，电可用于形成官能化的氟烷基自由基。由此，我们获得了具有良好官能团耐受性以及化学和区域选择性的各种二氟和单氟烷基产物。同样，α-羰基烷基溴化物的脱氟烯丙基化也被证明是可行的。通过实验和计算建立了反应机理。
