Nucleophilic and Radical Heptafluoroisopropoxylation with Redox‐Active Reagents

AbstractThe heptafluoroisopropyl group (CF(CF3)2) is prevalent in pharmaceuticals and agrichemicals. However, heptafluoroisopropoxylated (OCF(CF3)2) compounds remain largely underexplored, presumably due to the lack of efficient access to these compounds. Herein, we disclose the practical and efficient heptafluoroisopropoxylation reactions through the invention of a series of redox‐activeN‐OCF(CF3)2reagents. These reagents were readily prepared from the oxidative heptafluoroisopropylation of hydroxylamines with AgCF(CF3)2. The substitutions on the nitrogen atom significantly affected the properties and reactivities ofN‐OCF(CF3)2reagents. Accordingly, two types ofN‐OCF(CF3)2reagents includingN‐OCF(CF3)2phthalimideAandN‐OCF(CF3)2benzotriazolium saltO′were used as OCF(CF3)2anion and radical precursors, respectively. This protocol enables the direct heptafluoroisopropoxylation of a range of substrates, delivering the corresponding products in moderate to excellent yields.