Nucleophilic and Radical Heptafluoroisopropoxylation with Redox-Active Reagents.

The heptafluoroisopropyl group (CF(CF ) ) is prevalent in pharmaceuticals and agrichemicals. However, heptafluoroisopropoxylated (OCF(CF ) ) 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-active N-OCF(CF ) reagents. These reagents were readily prepared from the oxidative heptafluoroisopropylation of hydroxylamines with AgCF(CF ) . The substitutions on the nitrogen atom significantly affected the properties and reactivities of N-OCF(CF ) reagents. Accordingly, two types of N-OCF(CF ) reagents including N-OCF(CF ) phthalimide A and N-OCF(CF ) benzotriazolium salt O' were used as OCF(CF ) anion and radical precursors, respectively. This protocol enables the direct heptafluoroisopropoxylation of a range of substrates, delivering the corresponding products in moderate to excellent yields.