Fate of thianthrene in biological systems

Abstract

1. Thianthrene is a sulfur-containing tricyclic molecule distributed widely within the macrostructure of hydrocarbon fossil fuels. Identified nearly 150 years ago, its chemistry has been widely explored leading to insights into reaction mechanisms and radical ion formation. 2. It has been claimed to have therapeutic application in the treatment of dermal infections and to interfere with enzyme and nucleic acid function, but appears to have little toxicity. 3. Following its oral administration to the rat, the majority remained within the gastrointestinal tract. After three days, about 88% was detected in the combined excreta with the remainder still within the animal. It is readily taken up into fish from the surrounding aqueous environment and has been placed within the "bioaccumulative category" to be regarded with concern. 4. Mammalian metabolism appeared to be restricted to ring carbon oxidation and subsequent glucuronic acid conjugation. Small amounts of sulfoxide and disulfoxide were also formed. No ring degradation was evident. Microorganisms similarly undertook aromatic ring hydroxylation but were able also to rupture the ring system by attacking the carbon-sulfur linkages and thereby degrading the molecule.

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.…”

Diastereoselective Synthesis of Cyclopropanes from Carbon Pronucleophiles and Alkenes

“…Of note, this practical batch electrolysis reaction setup is comprised of a DC power supply, inexpensive electrodes, and a divided cell and does not require any precautions to exclude air or moisture. Combined with the low cost [102] low toxicity [103] and recyclability [67] of the thianthrene promoter, these results demonstrate the scalability of this electrochemical cyclopropanation protocol.…”

Electrogenerated thianthrenium conjugate enables (Z)-selective allylic amination

“…The reaction of thianthrenium cations with ubiquitous alkenes or alkynes to afford dicationic conjugates in a 1:1 or 2:1 stoichiometry was first described mechanistically in 1979 [6]. Thianthrene by itself is a readily available and biocompatible reagent [7] that can be recycled within the process, as previously described by the same research group [8]. However, it took several decades until synthetic organic chemists recognized the potential of this powerful redox reagent and decided to repurpose its use in recent methodology.…”