Trifluoromethyl Thianthrenium Triflate: A Readily Available Trifluoromethylating Reagent with Formal CF₃⁺, CF₃^•, and CF₃^– Reactivity

Abstract

Here we report the synthesis and application of trifluoromethyl thianthrenium triflate (TT-CF 3 + OTf − ) as a novel trifluoromethylating reagent, which is conveniently accessible in a single step from thianthrene and triflic anhydride. We demonstrate the use of TT-CF 3 + OTf − in electrophilic, radical, and nucleophilic trifluoromethylation reactions.

Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines

“…We recently developed an electrochemical strategy to engage oxidatively sensitive nucleophiles in net oxidative alkene difunctionalization reactions . Our approach draws inspiration from Yoshida’s pioneering cation pool work − and contributes to a rapidly growing body of literature exploiting oxidized thianthrene derivatives as synthetic intermediates. − Specifically, we leveraged electrochemistry to cleanly generate dicationic adducts between unactivated alkenes and thianthrene ( TT ), , a safe and inexpensive reagent. This strategy circumvents the need for oxidatively stable coupling partners in net oxidative alkene functionalization reactions; the oxidative alkene activation event is decoupled from nucleophilic substitution.…”

Copper‐Catalyzed 1,2‐Trifluoromethylation Carbonylation of Unactivated Alkenes: Efficient Access to β‐Trifluoromethylated Aliphatic Carboxylic Acid Derivatives

“…Based on the above results and related literature, [3,10,17] In summary, we have developed a novel procedure on carbonylative trifluoromethylation of unactivated alkenes. Catalyzed by copper catalyst, carbonylative difunctionaliza-tion of alkenes with Togin-CF 3 and nitrogen (or oxygen) nucleophiles occurred successfully.…”

“…[6] Among the limited achievements, Ding and co-workers reported a rhodium-catalyzed asymmetric hydrogenation of a-or b-trifluoromethylated acrylic acids for their preparation in 2013. [7] In 2020, an original transformation on C(sp 3 )-H trifluoromethylation of unactivated alkanes using CF 3 -Cu III complex was established by Hongs group. [8] Very recently, Studers group realized a cascade radical alkene acyltrifluoromethylation with acid fluorides employing Langlois reagent as the CF 3 source (Scheme 2, a).…”

Copper‐Catalyzed 1,2‐Trifluoromethylation Carbonylation of Unactivated Alkenes: Efficient Access to β‐Trifluoromethylated Aliphatic Carboxylic Acid Derivatives

“…[2] In the past decades, significant progress have been achieved in the incorporation of CF 3 group into organic molecules. [3] In this context, b-trifluoromethylated carboxylic acid derivates constitute an important component of various bio-active drugs. [4] For example, btrifluoromethylated phenylpropionic acid derivatives have been used as agonists of human peroxisome proliferatoractivated receptor alpha (PPAR) (Scheme 1).…”