State‐of‐the‐Art in Electrophilic Trifluoromethylthiolation Reagents

Abstract

This work proposed a label‐free, cost‐effective and fairly sensitive electrogenerated chemiluminescence (ECL) strategy for the specific detection of lysozyme based on the hemin/G‐quadruplex hybrid. Gold nanoparticles were spread onto the chitosan thin‐film as substrate to adsorb thiolated captures: a hairpin‐structured DNA, integrating dual head‐tail connected functional domains: one aptamer sequence for lysozyme and the other for hemin (iron(III) proto‐porphyrin IX). In the presence of the both, the hairpin conformation unfolded and transformed into the hemin/G‐quadruplex motif, which quenched the ECL emission of underlaid quantum dots significantly via the consumption of dissolved oxygen as endogenous coreactant. This construction enabled a wide linear response to lysozyme, ranging from 20 pg·mL−1 to 5 µg·mL−1, with a detection limit as low as 4.95 pg·mL−1 (e.g. 9.4 pmol·L−1), demonstrating the prospective utilization of DNA technologies in bioanalysis.

Deoxytrifluoromethylthiolation and Selenylation of Alcohols by Using Benzothiazolium Reagents

“…With the highest reported Hansch parameter (p = 1.44) and strong electron-withdrawing properties (Hammett parameters: s m = 0.40, s p = 0.50), the trifluoromethylthio (SCF 3 )g roup in particular has emergeda sapromising substituent in pharmaceuticals that counterintuitively combines significant polarity with high lipophilicity. [2,3] By contrast, nucleophilic trifluoromethylthiolation reactions are typicallyp erformed by using only ah andfulo f À SCF 3 sources, such as AgSCF 3 ,C uSCF 3 ,a nd [Me 4 N]SCF 3 . As demonstratedi na number of impressive contributions, reagents such as N-(trifluoromethylthio)phthalimide, [2(2-iodophenyl)propan-2-yl)oxy]-(trifluoromethyl)sulfane and Billard's trifluoromethyl sulfenamides have opened up new mild synthetic routes towards SCF 3 -substituted molecules that were not accessible by using the previously availablet oxic gases F 3 CSÀCl and F 3 CSÀSCF 3 .…”

“…[2] The resurgence in interest in the SCF 3 group has been driven in large part by the introductiono fn ew reagents for electrophilic trifluoromethylthiolation. [2] In addition to their high cost, am ajor challenge associated with these reagents is the relative instability of the free À SCF 3 anion because b-eliminationo ff luoridec an outcompete the desired nucleophilic trifluoromethylthiolation process. [2,3] By contrast, nucleophilic trifluoromethylthiolation reactions are typicallyp erformed by using only ah andfulo f À SCF 3 sources, such as AgSCF 3 ,C uSCF 3 ,a nd [Me 4 N]SCF 3 .…”

Mechanistic Insights into the Decarboxylative Electrophilic Trifluoromethylthiolation of β‐Ketocarboxylic Acids

“…[6b] The choice of this SCF 3 donor was based on its high electrophilic power, which is superior to that of other N-SCF 3 reagents. [15] We screened three reaction parameters: the nature of the base, the solvent and the temperature. In acetonitrile, inorganic bases [K 2 CO 3 or NaHCO 3 (1.2-1.5 equiv.)]…”

Merging Visible‐Light Catalysis for the Direct Late‐Stage Group‐16–Trifluoromethyl Bond Formation

“…The SCF 3 group is by far the most studied motif in the series of trifluoromethylchalcogen groups, probably due to the presence of different sources of SCF 3 , electrophilic, nucleophilic as well as radical sources –. In addition to the developed methodologies, the use of photoredox catalysis emerged recently to complement the toolbox .…”