50667-83-9Relevant articles and documents
Iron(II)/Persulfate Mediated Newman-Kwart Rearrangement
Gendron, Thibault,Pereira, Raul,Abdi, Hafsa Y.,Witney, Timothy H.,?rstad, Erik
supporting information, p. 274 - 278 (2020/01/02)
Herein, we report that iron(II)/ammonium persulfate in aqueous acetonitrile mediates the Newman-Kwart rearrangement of O-aryl carbamothioates. Electron-rich substrates react rapidly under moderate heating to afford the rearranged products in excellent yie
Electrochemically Catalyzed Newman-Kwart Rearrangement: Mechanism, Structure-Reactivity Relationship, and Parallels to Photoredox Catalysis
Roesel, Arend F.,Ugandi, Mihkel,Huyen, Nguyen Thi Thu,Májek, Michal,Broese, Timo,Roemelt, Michael,Francke, Robert
, p. 8029 - 8044 (2020/07/25)
The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as "electrochemical catalysis", is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman-Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental-quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.
Palladium-catalyzed intramolecular oxidative C-H sulfuration of aryl thiocarbamates
Zhao, Yingwei,Xie, Yinjun,Xia, Chungu,Huang, Hanmin
supporting information, p. 2471 - 2476 (2014/09/17)
A palladium-catalyzed intramolecular C-H bond sulfuration reaction of aryl thiocarbamates has been developed. This strategy provides a new route to benzo[d][1,3]oxathiol-2-ones with tolerance of a wide range of substituents. Mechanistic studies suggested