13511-97-2Relevant articles and documents
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.
Inverting the Selectivity of the Newman-Kwart Rearrangement via One Electron Oxidation at Room Temperature
Pedersen, Stephan K.,Ulfkj?r, Anne,Newman, Madeleine N.,Yogarasa, Sarangki,Petersen, Anne U.,S?lling, Theis I.,Pittelkow, Michael
, p. 12000 - 12006 (2018/09/25)
The discovery that the Newman-Kwart rearrangement can be performed at room temperature by action of a simple and readily available oxidant, cerium ammonium nitrate, is described. The conditions give clean conversion when using electron-rich aromatic subst
Cu(OAc)Catalyzed Thiolation of Acyl C-H bonds with thiols using TBHP as an oxidant
Yuan, Yan-Qin,Guo, Sheng-Rong,Xiang, Jian-Nan
supporting information, p. 443 - 448 (2013/03/29)
Cu(OAc)promoted TBHP oxidative coupling reaction of formamides with thiols successfully proceeded through direct C-H bond activation of formamides. The corresponding S-phenyl dialkyl thiocarbamate compounds were formed with high yield under solvent-free c