Recent advances in trifluoromethylthiolation using nucleophilic trifluoromethylthiolating reagents

Synthesis of Alpha‐trifluoromethylthio Carbonyl Compounds: A Survey of the Methods for the Direct Introduction of the SCF3 Group on to Organic Molecules

“…Only few examples of trifluoromethylthio-functionalization are known and generally involvet he use of nucleophilic [11] or electrophilic trifluoromethylthiolating reagents, where the SCF 3 ion can be generateds tartingf rom easy synthesizablep recursors (Scheme 1). Only few examples of trifluoromethylthio-functionalization are known and generally involvet he use of nucleophilic [11] or electrophilic trifluoromethylthiolating reagents, where the SCF 3 ion can be generateds tartingf rom easy synthesizablep recursors (Scheme 1).…”

Synthesis of trifluoromethylthiolated azacalix[1]arene[3]pyridines from the Cu(ii)-mediated direct trifluoromethylthiolation reaction of arenes via reactive arylcopper(iii) intermediates

“…[12][13][14][15][16] Nucleophilic aromatic substitution of aryl halides with various trifluoromethanethiolate sources such as CuSCF 3 constitutes a conventional method to construct aryl trifluoromethyl sulfides. Aryl trifluoromethyl sulfide compounds have found applications in agrochemical and materials science.…”

“…Aryl trifluoromethyl sulfide compounds have found applications in agrochemical and materials science. [13][14][15] For example, electrophilic N-trifluoromethylthiosaccharin has been reported to trifluoromethylthiolate a variety of electron-rich aromatic compounds when chlorotrimethylsilane or triflic acid is used as an activator. [12][13][14][15][16] Nucleophilic aromatic substitution of aryl halides with various trifluoromethanethiolate sources such as CuSCF 3 constitutes a conventional method to construct aryl trifluoromethyl sulfides.…”

“…12,15 Noticeably, with the advent of easy-to-use trifluoromethylthiolating reagents, direct trifluoromethylthiolation has gained increasing popularity. [12][13][14][15][16] The formidable challenges in mechanistic elucidation include, if not all, the isolation or observation of structurally well-defined organometallic intermediates. 17 Catalyzed by transition metals, trifluoromethanesulfenates, 18 N-trifluoromethylthiol phthalimide, 19,20 S 8 /CF 3 SiMe 3 21 and Me 4 NSCF 3 22 are able to react with arylboronic acids to form trifluoromethylthiolated arenes.…”

An Unconventional Mechanistic Insight into SCF3 Formation from Difluorocarbene: Preparation of 18F‐Labeled α‐SCF3 Carbonyl Compounds

“…A quick survey of reaction parameters finally revealed that an efficient transformation of our testing substrate, 2-bromoacetophenone with PDFA/S 8 /CsF system was achieved in 74% yield by the addition of CuBr 2 . We proposed that Cu-promoted trifluoromethylthiolation reactions occurred via ligand exchange of SCF 3 − with copper source to generate [CuSCF 3 ] complex, [17,18] followed by addition-reductive elimination to furnish final SCF 3 products. Indeed, we have observed [CuSCF 3 ] complex by 19 F NMR spectrometry in the trifluoromethylthiolation reaction systems (SI, section 5), further supporting this proposed reaction pathway.…”