Aliphatic compounds substituted with medicinally importantt rifluoromethylthio (SCF 3 )a nd trifluoromethylselenyl (SeCF 3 )g roups weres ynthesized directly from alcohols by using the new benzothiazolium salts BT-SCF 3 and BT-SeCF 3 .T hese bench-stable fluorine-containing reagents are facile to use and can be prepared in two steps from non-fluorinated heteroaromatic startingm aterials. The metal-free deoxytrifluoromethylthiolation process using BT-SCF 3 proceeds under mild conditions and the similarly efficient trifluoromethylselenylationr eactions using BT-SeCF 3 are, to the besto fo ur knowledge, the first reported examples of this transformation.Scheme1.a) Benzothiazolium Reagents BT-SCF 3 and BT-SeCF 3 .b )Previously reported deoxytrifluoromethylthiolation reactionso fa liphatic alcohols. c) This work: Deoxytrifluoromethylthiolation and selenylation of alcohols with BT-SCF 3 and BT-SeCF 3 .[bmim] = 1-Butyl-3-methylimidazolium.[a] S.Scheme2.a) Two-step synthesisofBT-SCF 3 and its applicationi nthe deoxytrifluoromethylthiolation of aliphatic alcohol 2a.b)Likely reaction mechanism via 2-alkoxybenzothiazolium salt 4.

Deoxygenative syntheses of fluorinated thioesters directly from carboxylic acids have been developed employing benzothiazolium reagents. The process using BT-SCF3 represents an attractive approach toward these SCF3-containing compounds that avoids the use of metal –SCF3 salts or preactivated acyl electrophiles. Moreover, the in situ activation of BT-SCF2H allows for an unprecedented nucleophilic difluoromethylthiolation reaction. DFT calculations support a mechanistic scenario involving a four-membered transition state where acyl substitution occurs without the formation of an unstable free –SCF2H anion.

Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro‐ and medicinal chemistry. Radical C−H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing .OCF3 radical sources make them unsuitable for the large‐scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one‐step synthesis of valuable pyridine derivatives, which have been previously prepared via multi‐step approaches.

A series of 2-(perfluoroalkylthio)benzothiazolium (BT-SRF) salts have been synthesized that serve as convenient sources of hitherto underexplored perfluoroalkylthiolate anions. An investigation of their reactivity in a deoxygenative nucleophilic substitution reaction led to the development of an unprecedented process that provides pentafluoroethyl and heptafluoropropyl thioethers directly from readily available alcohols.

The benzothiazolium salt BT-SeCF2H is introduced as an efficient nucleophilic reagent for transferring difluoromethylselenyl groups onto organic molecules. SeCF2H-Containing selenoesters could be prepared upon deoxygenative substitution of readily available carboxylic...