Csenki János T, Tóth Balázs L, Béke Ferenc, Varga Bálint, P Fehér Péter, Stirling András, Czégény Zsuzsanna, Bényei Attila, Novák Zoltán
ELTE "Lendület" Catalysis and Organic Synthesis Research Group Department, Institute of Chemistry, Eötvös Loránd University, Pázmány Péter stny. 1/A, 1117, Budapest, Hungary.
Research Centre for Natural Sciences, Eötvös Loránd Research Network, Magyar Tudósok körútja 2, 1117, Budapest, Hungary.
Angew Chem Int Ed Engl. 2022 Sep 12;61(37):e202208420. doi: 10.1002/anie.202208420. Epub 2022 Aug 9.
[1,2]-shift of atoms in alkyl fragments belongs to the class of dyotropic rearrangements. Various atoms, including halogens can be involved in the migration, however participation of iodine is unprecedented. Herein, we report our experimental and DFT studies on the oxidation triggered dyotropic rearrangement of iodo and chloro functions via butterfly-type transition state to demonstrate the migrating ability of λ -iodane centre. With the exploitation of dyotropic rearrangement we designed and synthesized a novel fluoroalkyl iodonium reagent from industrial feedstock gas HFO-1234yf. We demonstrated that the hypervalent reagent serves as an excellent fluoroalkylation agent for various amines and nitrogen heterocycles.
烷基片段中原子的[1,2]迁移属于双变重排类别。包括卤素在内的各种原子都可能参与迁移，然而碘的参与却是前所未有的。在此，我们报告了关于通过蝴蝶型过渡态由氧化引发的碘代和氯代官能团双变重排的实验和密度泛函理论（DFT）研究，以证明λ-碘鎓中心的迁移能力。通过利用双变重排，我们从工业原料气HFO-1234yf设计并合成了一种新型氟烷基碘鎓试剂。我们证明了这种高价试剂是用于各种胺类和氮杂环的优良氟烷基化试剂。
