Copper‐Catalyzed Trifluoromethylthiolation of Di(hetero)aryl‐λ³‐iodanes: Mechanistic Insight and Application to Synthesis of (Hetero)Aryl Trifluoromethyl Sulfides

Abstract

Thed irect andr egioselective copper/S-Phos-catalyzedt rifluoromethylthiolation of symmetrical andu nsymmetrical di(hetero)aryl-l 3 -iodanes has been accomplishedf or the synthesiso fv arious (hetero)aryl trifluoromethyl sulfides employingr eadily accessible silver trifluoromethylthiolate (AgSCF 3 ) as nucleophilict rifluoromethylthiolating reagent. Thed eveloped transformation tolerates various functional groups like nitrile, enolizable ketone,e ster, nitro andf ree carboxylic acid. Interestingly,t he formal trifluoromethylthiolation of arenes was also achieved through integration of the synthesis of diaryl-l 3 -iodanes from arenes with the trifluorome-thylthiolation. Mechanistic investigations did not favor the radical formation and SET pathway.B ased on the variable temperature 19 FNMR spectroscopy, isolation of the most relevant catalytic intermediate, and stoichiometrics tudies supported the Cu(I)/ Cu(III) catalytic cycle,w herein the oxidative addition of diaryl-l 3 -iodanesw as assisted by the silver salt.

Trifluoromethylthiolation of Unsymmetrical λ3‐Iodane Derivatives: Additive‐Free, Selective and Scalable Introduction of the SCF3 Group

“…We have developed a novel method for the Cu‐mediated C–SCF 3 bond‐forming reaction 16. Extensive investigations showed that no ligand and additives are necessary.…”

Mechanochemical Transformation of CF3 Group: Synthesis of Amides and Schiff Bases

“…Isolation of obtained compounds was achieved by column chromatography on Silica gel. Noncommercially available CF 3 , [23] CF 2 , [24] and NO 2 [25] substrates were prepared according to the known literature. All commercially available compounds were purchased from appropriate vendors.…”

Palladium‐Catalyzed Trifluoromethylthiolation of Chelation‐Assisted C–H Bonds

“…Recently, Billard and co‐workers developed a one‐step process to various N‐SCF 3 reagents from readily available amines, diethylaminosulfur trifluoride (DAST) and CF 3 TMS, which are also shown to be excellent electrophilic SCF 3 sources. Our long‐standing interest in the synthesis of trifluoromethylthiolated arenes and C–H bond functionalization, as well as the importance of trifluoromethylthiolated arenes, in combination with easy access to N‐SCF 3 reagents through Billard's protocol prompted us to develop a direct trifluoromethylthiolation of C–H bonds employing a readily accessible reagent . Thus, we herein disclose the palladium‐catalyzed trifluoromethylthiolation of chelation‐assisted C–H bonds of arenes (Scheme b).…”