With the best set of conditions in hand, we evaluated the effectiveness of the protocol to different isothiocyanates starting materials. Initial tests were devoted to subjecting benzylic isothiocyanate to our reaction conditions. The desired compounds were obtained from low to very good yields (Scheme 2, products 3a-c). Afterwards, aliphatic isothiocyanates were exposed to the reaction conditions and proved compatible with yields up to 67% (Scheme 2, products 3d-3i). Noteworthy, Melatonin precursor derivative (Scheme 2, compound 3d) was derivatized in a synthetically useful isolated yield of 35%. Several protected tertiary amines were also found to be effective under the reaction conditions (Scheme 2, products 3g-3i). Next, aromatic isothiocyanates were evaluated. Electron rich aryl starting material were tolerated using our protocol and the desired products were obtained with yields up to 78% (Scheme 2, products 3j-3q). It should be mentioned that ortho, meta or para substituted isothiocyanates are suitable partners. Interestingly, the structure of 3m was unambiguously confirmed by X-ray crystallographic analysis. Afterwards, we evaluated the influence of electron withdrawing substituents on the starting aryl isothiocyanate derivatives. The para substituted phenylisothiocyanate with a phenyl ring furnishes the desired product in 67% yield (Scheme 2, 3r). Unfortunately, the presence of strong electron withdrawing groups including NO2, CN or fluorine were detrimental to the reaction and no product formation was observed (Scheme 2, products 3s-3u) probably due to a decrease of the nucleophilicity of the resulting trifluoromethyl amine anion intermediate. Knowing that Shen's reagent would be too electrophilic (vide supra) and based on the relative trifluoromethylthio cation-donating scale, we identified trifluoromethylthio dimer ((SCF3)2) as the most promising reagent to employ. In addition, the in situ generation of such a reactive species has been well documented in the literature. 4a Indeed, the Langlois reagent can react with phosphine derivatives to yield to nucleophilic SCF3 which can easily be oxidized to the desired dimer. Disappointingly, our initial in situ test turned out to be ineffective. Aware of the incompatibly issues that could arise from mixing together of all the reaction components, we decided to use a two-chamber reactor. In chamber 1, formation of -SCF3 anion was obtained by reacting chloro diphenylphosphine with the Langlois reagent. This unstable anion readily collapses to difluorophosgene gas which is trapped in the second chamber by AgF yielding to AgSCF3. The formation of nucleophilic trifluoromethylamine through fluorinative desulfurization with AgF also yield to Ag2S byproduct that could potentially oxidize AgSCF3 to afford trifluoromethylthio dimer ((SCF3)2). Our hypothesis turned out to be effective when isothiocyanate was mixed with silver fluoride in the first chamber while Langlois's reagent reacted with PPh2Cl in the second chamber. Under these conditions, electron poor arenes including NO2, CN, CF3, acetyl, ester could be transformed to the desired products with isolated yields up to 80% (Scheme 2, products 3s-3r). Halogen substituted arenes including bromo and fluoro derivatives were also obtained in excellent yields of 70% and 75%, respectively (Scheme 2, products 3z, 3u). Naphthalene derivative 3aa was obtained in 72% yield. Finally, we decided to assess this protocol to electron donating arene derivatives as well as to aliphatic compounds to offer a complementary approach to the original one (Conditions A) using commercially available reagents. It turns out that these new conditions are also effective with electron donating aryl isocyanates derivatives and the desired products are formed with very good yields up to 90% (Scheme 2, products 3ab, 3j-m). Herein also diarylether derivatives substituted with halogens, including: fluoro, chloro and bromo were tolerated and the desired products were obtained in an excellent yield up to 90% (Scheme 2, products 3ab, 3ac & 3ad). Moreover, aliphatic product 3g was also obtained in good yield (60%) while the penicillin core structure was derivatized in a synthetically useful yield of 33% (Scheme 2, product 3af). Finally, the robustness of our strategy was further demonstrated starting with other complex structure. Indeed, using DL-Menthol derivatives allow to obtain the desired product 3ag in good isolated yield of 56%. Also, using the diacetonefructose derivatives allows the formation of the compound 3ah in very good yield. Finally, vitamin E derivatives 3ai was obtained with an excellent yield of 83% when the reaction was performed in a mixture of ether/MeCN to increase the solubility of the starting 1ai.