The activation of SF6, a potent greenhouse gas, under metal‐free and visible light conditions is reported. Herein, mechanistic investigations including EPR spectroscopy, NMR studies and cyclic voltammetry allowed the rational design of a new fluorinating reagent which was synthesized from the 2‐electron activation of SF6 with commercially available TDAE. This new SF5‐based reagent was efficiently employed for the deoxyfluorination of CO2 and the fluorinative desulfurization of CS2 allowing the formation of useful fluorinated amines. Moreover, for the first time we demonstrated that our SF5‐based reagent could afford the mild generation of Cl‐SF5 gas. This finding was exploited for the chloro‐pentafluorosulfanylation of alkynes and alkenes.
The selective one-step access to fluoroalkylated hexestrol derivatives, nonsteroidal estrogens, is achieved in good to excellent isolated yields under organophotoredox conditions by using the stable and easy to handle Langlois reagent.Furthermore, the challenging selective hydrotrifluoromethylation of styrenes proceeds under mild reaction conditions without the requirement for any additive. We assume that the solvent drives the reaction pathway towards either the reduction or the dimerization of the radical intermediate generated after initial addition of the fluoroalkyl radical to the styrene. The versatility of the developed system is also extended to encompass radical-radical cross-coupling as exemplified here using cyanopyridine. Mechanistic investigations including luminescence and EPR spectroscopy allow to shed the light on the different mechanisms.
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