Abstract

The utility of pentafluorosulfanyl (SF₅)-containing compounds has been limited because the chemistry has not been fully explored. While significant attention has been focused on the incorporation of fluorine in C-F bonds, or the introduction of a trifluoromethyl (CF₃) groups, our attention has been focused on the SF₅ group. The SF₅ group has a similar electron withdrawing effect as the CF₃ group yet the SF₅ group is significantly more lipophilic. Combining these properties results in the proclivity of SF₅-containing arenes to undergo displacement reactions. The hydrophobicity of the SF₅-group was used to direct the conformation of SF₅-containing peptides. The profound dipole associated with pentafluorosulfanylation has been successfully used to direct the stereochemistry of the Staudinger reaction. The greater steric demand of the SF₅ group relative to the CF₃ group has dramatically effected the conformation of small molecules by encumbering rotational freedom. The influence of the SF₅-group on the reactions of alkanes, alkenes, alkynes, arenes and various functional groups is reviewed below.

Keywords: Fluorine, fluoroalkyl group, pentafluorosulfanyl group, substituent effects, sulfur.

Graphical Abstract