Alkene 1,3-Difluorination via Transient Oxonium Intermediates

Angew Chem Int Ed Engl. 2024 May 2:e202404666. doi: 10.1002/anie.202404666. Online ahead of print.ABSTRACTThe 1,3-difunctionalization of unactivated alkenes is an under-explored transformation that leads to moieties that are otherwise challenging to prepare. Herein, we report a hypervalent iodine-mediated 1,3-difluorination of homoallylic (aryl) ethers to give unreported 1,3-difluoro-4-oxy groups with moderate to excellent diastereoselectivity. The transformation proceeds through a different mode of reactivity for 1,3-difunctionalization, in which a regioselective addition of fluoride opens a transiently formed oxonium intermediate to rearrange an alkyl chain. The optimized protocol is scalable and shown to proceed well with a variety of functional groups and substitution on the alkenyl chain, hence providing ready access to this fluorinated, conformationally controlled moiety.PMID:38695434 | DOI:10.1002/anie.202404666

Source: Angewandte Chemie - May 2, 2024 Category: Chemistry Authors: Alice C Dean E Harvey Randle Andrew J D Lacey Guiherme A Marczak Giorio Sayad Doobary Benjamin D Cons Alastair Lennox Source Type: research