Unusual Single Electron Transfer Reactions between Alkenes and Iodine Electrophiles†

Comprehensive Summary The electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis. The organic chemistry textbook describes the classical reaction between an alkene and an iodine electrophile (such as elemental iodine and N ‐iodosuccinimide (NIS)) as a typical ionic reaction, in which an iodonium ion is formed and then attacked by a nucleophile. However, in this article, we report a new and unusual reaction mode between an alkene and NIS; that is, a single electron transfer (SET) process occurs between these two reactants by forming an electron‐donor acceptor complex. Not only does this unusual single electron transfer reaction between an alkene and NIS add fundamentally important knowledge to organic chemistry, it also provides a valuable synthetic method as the new SET reaction mode with opposite regioselectivity as compared with the traditional ionic mode.