Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF₃

Abstract

Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert–Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.

Reductive thiolation and oxidative dehydroaromatization of cyclohexanones with primary amines and sodium sulfinates to access o-sulfanylanilines

“…3 Additionally, sodium sulfinates can be used as an alternative sulfur source to unstable and rotten thiols to prepare thioether compounds under reduction conditions. 4 In recent years, C–H thiolation of (hetero)arenes or reductive cross-coupling with aryl halides has been documented to prepare aryl sulfides utilizing sodium sulfinates as sulfenylating reagents. 5 These reported transformations require excess amounts of reducing agents or expensive transition-metal catalysts.…”

Access to α-Hydroxy Amides via a Practical Metal-Free “One-Pot” Tandem Reaction Involving Aerobic C(sp3)–H Hydroxylation and C(sp2)–C(sp3) Cleavage

“…Despite such advance in ingenious α-hydroxylation of amides, the obstacle still lay ahead. The N –H bond is easy to be deprotonated to affect the α-C–H oxidation of simple N -aryl amides. , Therefore, we introduced a new indirect approach to address these challenges. The acyl group could be installed to enhance α-C–H acidity.…”

Copper-promoted indirect trifluoromethylthiolation of sulfuryl chloride with TMSCF3: facile access to trifluoromethyl thioethers

“…Recently, we developed a new synthetic method of aryl trifluoromethyl thioethers using Ruppert-Prakash reagent and sodium arylsulfinate as starting substrates, through a diphenyl disulfide intermediate. 49 However, the synthetic method was restricted to sodium arylsulfinate as the substrate for the synthesis of aryl trifluoromethyl thioethers at a high temperature of 100 1C. Inspired by the deoxygenation of sulfonyl chlorides for electrophilic sulfenylation, 50 we tried to develop a more efficient method for the synthesis of trifluoromethyl thioethers.…”