5818-99-5Relevant 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.
Modelling the Inhibition of Selenoproteins by Small Molecules Using Cysteine and Selenocysteine Derivatives
Reddy, Kishorkumar M.,Mugesh, Govindasamy
, p. 8875 - 8883 (2019/06/17)
Small molecule-based electrophilic compounds such as 1-chloro-2,4-dinitrobenzene (CDNB) and 1-chloro-4-nitrobenzene (CNB) are currently being used as inhibitors of cysteine- and selenocysteine-containing proteins. CDNB has been used extensively to determine the activity of glutathione S-transferase and to deplete glutathione (GSH) in mammalian cells. Also, CDNB has been shown to irreversibly inhibit thioredoxin reductase (TrxR), a selenoenzyme that catalyses the reduction of thioredoxin (Trx). Mammalian TrxR has a C-terminal active site motif, Gly-Cys-Sec-Gly, and both the cysteine and selenocysteine residues could be the targets of the electrophilic reagents. In this paper we report on the stability of a series of cysteine and selenocysteine derivatives that can be considered as models for the selenoenzyme–inhibitor complexes. We show that these derivatives react with H2O2 to generate the corresponding selenoxides, which undergo spontaneous elimination to produce dehydroalanine. In contrast, the cysteine derivatives are stable towards such elimination reactions. We also demonstrate, for the first time, that the arylselenium species eliminated from the selenocysteine derivatives exhibit significant redox activity by catalysing the reduction of H2O2 in the presence of GSH (GPx (glutathione peroxidase)-like activity), which suggests that such redox modulatory activity of selenium compounds may have a significant effect on the cellular redox state during the inhibition of selenoproteins.
Selenomethoxylation of Alkenes Promoted by Oxone
Perin, Gelson,Santoni, Paolo,Barcellos, Angelita M.,Nobre, Patrick C.,Jacob, Raquel G.,Lenard?o, Eder J.,Santi, Claudio
, p. 1224 - 1229 (2018/03/21)
We describe herein an alternative method for the selenomethoxylation of unactivated alkenes using Oxone as a stoichiometric oxidant. The electrophilic species of selenium were easily generated in situ by the reaction of diorganyl diselenides with Oxone. By this efficient and simple approach, β-methoxy-selenides were obtained in moderate to excellent yields at room temperature in an open flask, starting from alkenes by using methanol as both nucleophile and solvent. When a mixture of H2O/CH3CN was employed as the solvent, β-hydroxy-selenides were selectively obtained under mild conditions.
Visible light-promoted, iodine-catalyzed selenoalkoxylation of olefins with diselenides and alcohols in the presence of hydrogen peroxide/air oxidant: an efficient access to α-alkoxyl selenides
Liu, Mingxuan,Li, Yiming,Yu, Lei,Xu, Qing,Jiang, Xuefeng
, p. 294 - 299 (2018/01/04)
Under iodine-catalyzed and visible light-irradiated aerobic conditions, selenoalkoxylation of olefins with diselenides and alcohols can be efficiently achieved to afford the useful α-alkoxyl selenides in the presence of only 0.5 equiv. of H2O2. Controlling the sub-stoichiometric H2O2 amount is crucial to avoid the non-selective over-oxidation of the diselenides that leads to the ineffective hyper-valent selenium compounds. Meanwhile, under visible light irradiation, the green, safe, and low-cost air can work as a supplemental mild oxidant in the reaction to ensure selective oxidation of the diselenides, full conversion of the reactants, and ultimately good yield of the products.
Green and Practical Oxidative Deoximation of Oximes to Ketones or Aldehydes with Hydrogen Peroxide/Air by Organoselenium Catalysis
Jing, Xiaobi,Yuan, Dandan,Yu, Lei
, p. 1194 - 1201 (2017/04/13)
Organoselenium-catalyzed oxidative deoximations afforded ketones and aldehydes under mild conditions. The reactions employ hydrogen peroxide and air as clean oxidants and lead to a waste-free and metal-free deprotection protocol for carbonyl protection strategies as well as the green synthesis of ketones and aldehydes. The mechanisms of this interesting organoselenium-catalyzed reaction have been investigated by control experiments as well as the selenium 77 nuclear magnetic resonance (77Se NMR) tests. This novel reaction largely expands the application scope of organoselenium catalysis. (Figure presented.).
A novel role of zeolite NaY in the thermal reaction of alkyl aryl selenoxides in its supercages
Zhang, Wanxuan,Yu, Haitao,Gao, Yu,Meng, Jiben,Matsuura, Teruo
, p. 498 - 499 (2007/10/03)
Thermal reaction of alkyl aryl selenoxides in the presence of water or methanol in the supercage of zeolite NaY gave β-hydroxy- or β-methoxyalkyl aryl selenides, respectively, and NaY played a novel role to stabilize reactive ArSeOH and to separate an anion of -OH from a carbonium ion which was simultaneously present with the -OH in a supercage.
HYDROLYTIC SELENOXIDE ELIMINATION REACTION FOR THE PREPARATION OF 2-CHLORO-1-OLEFINS
Engman, Lars
, p. 1463 - 1466 (2007/10/02)
2-Chloro-1-olefins were synthesized in a regiocontrolled way from terminal olefins by a sequence involving Markownikoff-addition of PhSeCl, chlorination of the resulting β-chloroalkyl phenyl selenides with SO2Cl2 and, after recrystallization, hydrolysis/s
A MECHANISM ON GENERATION AND RECYCLE OF THE SELENENYLATING REAGENTS IN ELECTROCHEMICAL OXYSELENENYLATION-DESELENENYLATION OF OLEFINS
Uneyama, Kenji,Ono, Michio,Torii, Sigeru
, p. 35 - 44 (2007/10/02)
The transformation of olefins 1 into allylic ethers and alcohols 2 (R = Me or H) was performed in 70-90percent yields, using a catalytic amount of diphenyl diselenide, by an electrochemical oxyselenenylation-deselenenylation sequence.The electrooxidation
