62885-97-6Relevant academic research and scientific papers
The polyhedral nature of selenium-catalysed reactions: Se(iv) species instead of Se(vi) species make the difference in the on water selenium-mediated oxidation of arylamines
Capperucci, Antonella,Dalia, Camilla,Tanini, Damiano
, p. 5680 - 5686 (2021/08/16)
Selenium-catalysed oxidations are highly sought after in organic synthesis and biology. Herein, we report our studies on the on water selenium mediated oxidation of anilines. In the presence of diphenyl diselenide or benzeneseleninic acid, anilines react with hydrogen peroxide, providing direct and selective access to nitroarenes. On the other hand, the use of selenium dioxide or sodium selenite leads to azoxyarenes. Careful mechanistic analysis and 77Se NMR studies revealed that only Se(iv) species, such as benzeneperoxyseleninic acid, are the active oxidants involved in the catalytic cycle operating in water and leading to nitroarenes. While other selenium-catalysed oxidations occurring in organic solvents have been recently demonstrated to proceed through Se(vi) key intermediates, the on water oxidation of anilines to nitroarenes does not. These findings shed new light on the multifaceted nature of organoselenium-catalysed transformations and open new directions to exploit selenium-based catalysis.
The Unexpected Role of SeVI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide
Back, Thomas G.,Gelfand, Benjamin S.,George, Graham N.,Mendoza Rengifo, Emerita,Pickering, Ingrid J.,Sands, Kai N.
supporting information, p. 4283 - 4287 (2020/02/11)
Benzeneperoxyseleninic acid has been proposed as the key intermediate in the widely used epoxidation of alkenes with benzeneseleninic acid and hydrogen peroxide. However, it reacts sluggishly with cyclooctene and instead rapidly decomposes in solution to
Facile synthesis of 2-methylenecyclobutanones via Ca(OH) 2-catalyzed direct condensation of cyclobutanone with aldehydes and (PhSe)2-catalyzed Baeyer-Villiger oxidation to 4-methylenebutanolides
Yu, Lei,Wu, Yulan,Cao, Hongen,Zhang, Xu,Shi, Xinkang,Luan, Jie,Chen, Tian,Pan, Yi,Xu, Qing
, p. 287 - 293 (2014/01/06)
2-Methylenecyclobutanones (2-MCBones), used to be difficult to access, but can now be easily achieved by a green and stereospecific Ca(OH) 2-catalyzed direct and simple aldol condensation of cyclobutanone and aldehydes under mild conditions. The obtained (E)-2-MCBones should be a class of potentially useful building blocks in synthesis as they could readily undergo an interesting (PhSe)2-catalyzed Baeyer-Villiger (BV) oxidation with H2O2 at room temperature to give the versatile 4-methylenebutanolides. Mechanistic studies revealed that the BV reaction most possibly proceeded via the initial formation of benzeneseleninoperoxoic anhydride [PhSe(O)O]2O, which then converted to benzeneseleninoperoxoic acid PhSe(O)OOH as the active oxidant, followed by its selective addition to the CO bond of 2-MCBones and then a selective C-C bond cleavage and rearrangement to give 4-methylenebutanolides.
BENZENEPEROXYSELENINIC ACIDS - SYNTHESIS AND PROPERTIES
Syper, Ludwik,Mlochowski, Jacek
, p. 207 - 214 (2007/10/02)
Benzeneperoxyseleninic acid (3) and its analogs, 2-nitro and 2,4-dinitrobenzeneperoxyseleninic acids (10, 11), were obtained by oxidation of corresponding arylseleninic acids or diaryldiselenides with hydrogen peroxide.Their chemical properties were studied and rearrangement of 3 to benzeneselenic acid 7 was found as an useful method for preparation of this compound.It was also shown that peroxyseleninic acid 10 can be used as an efficient oxidant in the Baeyer-Villiger transformation of the formyl group into formyloxy one.
