69734-16-3Relevant academic research and scientific papers
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)
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
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.
An Electrocatalytic Newman-Kwart-type Rearrangement
Broese, Timo,Roesel, Arend F.,Prudlik, Adrian,Francke, Robert
supporting information, p. 7483 - 7487 (2019/01/03)
An electrochemical approach toward rearrangement of O-aryl thiocarbamates to the corresponding S-aryl thiocarbamates is presented. The protocol requires only catalytic amounts of electric charge and allows for operation at room temperature. The electrolys
2,6-diaryl pyridazinones with immunosuppressant activity
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, (2008/06/13)
A class of 2,6-diarylpyridazinones of general structural formula I have been identified that exhibit exhibit immunosuppressant activity with human T-lymphocytes, and are useful as an immunosuppressants. STR1 or a pharmaceutically acceptable salt, hydrate or crystal form thereof
Infrared Spectra and Transmission of Electronic Effects in Substituted Phenyl N,N-Dimethylcarbamates and S-Phenyl N,N-Dimethylthiocarbamates
Perjessy, Alexander,Jones, Ronald G.,McClair, Susan L.,Wilkins, Joyce M.
, p. 1266 - 1271 (2007/10/02)
Carbonyl stretching frequencies in CCl4 and CHCl3 and hydroxyl stretching frequency shifts of phenol as a proton donor in CCl4 were measured for series of substituted phenyl N,N-dimethylcarbamates (I) and S-phenyl N,N-dimethylthiocarbamates (II).The data
