F. Qing, Chaolai Tong, Xiuhua Xu
Aug 19, 2021
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Influential Citations
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Journal
Angewandte Chemie
Abstract
The heptafluoroisopropyl group (CF(CF 3 ) 2 ) is prevalent in pharmaceuticals and agrichemicals. However, the heptafluoroisopropoxylated (OCF(CF 3 ) 2 ) biologically interesting 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 3 ) 2 reagents. These reagents were readily prepared from the oxidative heptafluoroisopropylation of hydroxylamines with AgCF(CF 3 ) 2 . The substitutions on the nitrogen atom significantly affected the properties and reactivities of N -OCF(CF 3 ) 2 reagents. Accordingly, two types of N -OCF(CF 3 ) 2 reagents including N -OCF(CF 3 ) 2 phthalimide A and N -OCF(CF 3 ) 2 benzotriazolium salt O' were used as OCF(CF 3 ) 2 anion and radical precursors, respectively. This protocol enables the direct heptafluoroisopropoxylation of a range of substrates, such as alkyl halides, alcohols, alkenes, and (hetero)arenes, delivering the corresponding heptafluoroisopropoxylated products in moderate to excellent yields. Furthermore, the late-stage heptafluoroisopropoxylation of pharmaceuticals and agrochemicals was also demonstrated. The X-ray single crystal diffraction analysis revealed that the dihedral angle of C Ar -O-CF(CF 3 ) 2 and aromatic planes was around 80° in aryl heptafluoroisopropyl ethers (ArOCF(CF 3 ) 2 ).