478399-10-9Relevant academic research and scientific papers
Sultam and sultim structures, part 2. Functionalized novel cyclic sulfin- and sulfonamides: A comparison of hydrogen bonding formation in sulfoxides and sulfones
Schulze, B?rbel,Taubert, Kathleen,Gelalcha, Feyissa Gadissa,Hartung, Christine,Sieler, Joachim
, p. 383 - 392 (2002)
The stable hydroperoxides rac-cis-2a,d and 4a,c were synthesized by oxidation of the salts 1. The 3-hydroxy sultims rac-cis-3a,b and sultams 5a,e were obtained by reduction of the corresponding hydroperoxides 2 and 4. Crystal structure analyses were perfo
Chemoselective electrophilic oxidation of heteroatoms by hydroperoxy sultamst
Gelalcha, Feyissa Gadissa,Schulze, Baerbel
, p. 8400 - 8406 (2007/10/03)
The synthesis of novel hydroperoxy sultams 1b-d and their potential as renewable chemoselective electrophilic oxidants for a wide range of nitrogen, sulfur, and phosphorus heteroatoms in nonaqueous media is described. Reactions of 1b,c with secondary amines 10f,g yielded the hydroxysultams 2b,c and nitrone 11f or radical 11g depending on the substrate and stoichiometry, while tertiary amines 10a-d gave amine oxides 11a-d. Compounds 1c,d oxidized various thioethers 12a-g to sulfoxides 13a-g smoothly that were isolated by chromatography in nearly quantitative yields. 1c was regenerated from 2c by treatment of the latter with acidified H2O2. Kinetic studies of the reaction of 1c with 1,4-thioxane 12f suggest that the reaction follows the second-order kinetics, first order in substrate and first order in oxidant with the second-order rate constant several orders of magnitude larger than that of the corresponding reaction with hydrogen peroxide and tert-butyl hydroperoxide without the need for any acid or heavy metal catalysts. The phosphines 14a,b were also oxidized by 1c to the respective phosphine oxides 15a,b readily in quantitative yields. The reactions may be conducted at ambient temperature or lower and appear to proceed via a nonradical mechanism. Reactions are sensitive to steric as well as electronic factors.
